Changbao Zhu

Reversible Storage of Lithium in Silver‐Coated Three‐Dimensional Macroporous Silicon

[*] Dr. Y. Yu, C. Zhu, Prof. Dr. J. Maier Max Planck Institute for Solid State Research Heisenbergstrasse 1, 70569 Stuttgart (Germany) E-mail: yan.yu@fkf.mpg.de Dr. L. Gu, Prof. S. Tsukimoto WPI Advanced Institute for Materials Research Tohoku University 2-1-1 Katahira Aoba-ku, Sendai 980-8577 (Japan) E-mail: gu@wpi-aimr.tohoku.ac.jp Dr. L. Gu, Dr. P. A. van Aken Stuttgart Center for Electron Microscopy Max Planck Institute for Metals Research Heisenbergstrasse 3, 70569 Stuttgart (Germany)

Tin Nanoparticles Encapsulated in Porous Multichannel Carbon Microtubes: Preparation by Single-Nozzle Electrospinning and Application as Anode Material for High-Performance Li-Based Batteries

Tin nanoparticles encapsulated in porous multichannel carbon microtubes (denoted as SPMCTs) were prepared by carbonization of electrospun PAN-PMMA-tin octoate nanofibers fabricated using a single-nozzle electrospinning technique. This material exhibited excellent characteristics for lithium ion battery anode applications in terms of reversible capacities, cycling performance, and rate capability. Undertaking such a production configuration allows the long-existing problem of obtaining a high packing density of tin particles while retaining sufficient spare space to buffer the volume variation during lithium alloying and dealloying processes to be properly addressed. Furthermore, the porous carbon shell preserves both the mechanical and chemical stability of the function-active Sn metal, which also serves as a highly conductive medium allowing Li(+) to access.

Carbon-Coated Na3V2(PO4)3 Embedded in Porous Carbon Matrix: An Ultrafast Na-Storage Cathode with the Potential of Outperforming Li Cathodes

Sodium ion batteries are one of the realistic promising alternatives to the lithium analogues. However, neither theoretical energy/power density nor the practical values reach the values of Li cathodes. Poorer performance is expected owing to larger size, larger mass, and lower cell voltage. Nonetheless, sodium ion batteries are considered to be practically relevant in view of the abundance of the element Na. The arguments in favor of Li and to the disadvantage of Na would be completely obsolete if the specific performance data of the latter would match the first. Here we present a cathode consisting of carbon-coated nanosized Na3V2(PO4)3 embedded in a porous carbon matrix, which not only matches but even outshines lithium cathodes under high rate conditions. It can be (dis)charged in 6 s with a current density as high as 22 A/g (200 C), still delivering a specific capacity of 44 mAh/g, while up to 20 C, the polarization is completely negligible.

Li Storage in 3D Nanoporous Au‐Supported Nanocrystalline Tin

3D nanoporous Au-supported nano-crystalline tin thin-film anodes for Li-ion batteries are prepared by dealloying followed by electroless plating. When used as an electrode for Li-ion batteries, this special Sn structure can effectively accommodate large volume variations during cycling in a lithium cell, resulting in improved capacity retention.

Direct Observation of Lithium Staging in Partially Delithiated LiFePO4 at Atomic Resolution

Lithium ions in LiFePO(4) were observed directly at atomic resolution by an aberration-corrected annular-bright-field scanning transmission electron microscopy technique. In addition, it was found in partially delithiated LiFePO(4) that the remaining lithium ions preferably occupy every second layer, along the b axis, analogously to the staging phenomenon observed in some layered intercalation compounds. This new finding challenges previously proposed LiFePO(4)/FePO(4) two-phase separation mechanisms.

Ge/C nanowires as high-capacity and long-life anode materials for Li-ion batteries.

Germanium-based materials (Ge and GeOx) have recently demonstrated excellent lithium-ion storage ability and are being considered as the most promising candidates to substitute commercial carbon-based anodes of lithium-ion batteries. Nevertheless, practical implementation of Ge-based materials to lithium-ion batteries is greatly hampered by the poor cyclability that resulted from the huge volume variation during lithiation/delithiation processes. Herein, uniform carbon-encapsulated Ge and GeOx nanowires were synthesized by a one-step controlled pyrolysis of organic-inorganic hybrid GeOx/ethylenediamine (GeOx/EDA) nanowires in H2/Ar and Ar atmospheres, respectively. The as-obtained Ge/C and GeOx/C nanowires possess well-defined 0D-in-1D morphology and homogeneous carbon encapsulation, which exhibit excellent Li storage properties including high specific capacities (approximate 1200 and 1000 mA h g(-1) at 0.2C for Ge/C and GeOx/C, respectively). The Ge/C nanowires, in particular, demonstrate superior rate capability with excellent capacity retention and stability (producing high stable discharge capacities of about 770 mA h g(-1) after 500 cycles at 10C), making them promising candidates for future electrodes for high-power Li-ion batteries. The improved electrochemical performance arises from synergistic effects of 0D-in-1D morphology and uniform carbon coating, which could effectively accommodate the huge volume change of Ge/GeOx during cycling and maintain perfect electrical conductivity throughout the electrode.

High Power-High Energy Sodium Battery Based on Threefold Interpenetrating Network.

A 3D tricontinuous Na3 V2 (PO4 )3 :reduced graphene oxide-carbon nanotube cathode is directly deposited on the current collector without any conductive additives or binders by a facile electrostatic spray deposition (ESD) technique. Such an electrode displays excellent rate capability and long cycling stability, which is rather typical of supercapacitors but is connected here with the much higher energy density of an efficient battery electrode.

A General Strategy to Fabricate Carbon-Coated 3D Porous Interconnected Metal Sulfides: Case Study of SnS/C Nanocomposite for High-Performance Lithium and Sodium Ion Batteries.

Transition metal sulfides have a great potential for energy storage due to the pronouncedly higher capacity (owing to conversion to metal or even alloy) than traditional insertion electrode materials. However, the poor cycling stability still limits the development and application in lithium and sodium ion batteries. Here, taking SnS as a model material, a novel general strategy is proposed to fabricate a 3D porous interconnected metal sulfide/carbon nanocomposite by the electrostatic spray deposition technique without adding any expensive carbonaceous materials such as graphene or carbon nanotube. In this way, small nanorods of SnS are generated with sizes of ≈10–20 nm embedded in amorphous carbon and self‐assembled into a 3D porous interconnected nanocomposite. The SnS:C is directly deposited on the Ti foil as a current collector and neither conductive additives nor binder are needed for battery assembly. Such electrodes exhibit a high reversible capacity, high rate capability, and long cycling stability for both lithium and sodium storage.

Phase Boundary Propagation in Large LiFePO4 Single Crystals on Delithiation

Large single crystals of LiFePO(4) have been chemically delithiated. The relevance of chemical oxidation in comparison with electrochemical delithiation is discussed. Analyses of the Li content and profiles were done by electron energy loss spectroscopy and secondary ion mass spectrometry. The propagation of the FePO(4) phase growing on the surface of the large single crystal was followed by in situ optical microscopy as a function of time. The kinetics were evaluated in terms of linear irreversible thermodynamics and found to be characterized by an induction period followed by parabolic growth behavior of the FePO(4) phase indicating transport control. The growth rate was shown to depend on the crystallographic orientation. Scanning electron microscopy images showed cracks and a high porosity of the FePO(4) layer due to the significant changes in the molar volumes. The transport was found to be greatly enhanced by the porosity and crack formation and hence greatly enhanced over pure bulk transport, a result which is supposed to be very relevant for battery research if coarse-grained powder is used.

Challenges and Perspectives for NASICON‐Type Electrode Materials for Advanced Sodium‐Ion Batteries

Sodium-ion batteries (SIBs) have attracted increasing attention in the past decades, because of high overall abundance of precursors, their even geographical distribution, and low cost. Apart from inherent thermodynamic disadvantages, SIBs have to overcome multiple kinetic problems, such as fast capacity decay, low rate capacities and low Coulombic efficiencies. A special case is sodium super ion conductor (NASICON)-based electrode materials as they exhibit - besides pronounced structural stability - exceptionally high ion conductivity, rendering them most promising for sodium storage. Owing to the limiting, comparatively low electronic conductivity, nano-structuring is a prerequisite for achieving satisfactory rate-capability. In this review, we analyze advantages and disadvantages of NASICON-type electrode materials and highlight electrode structure design principles for obtaining the desired electrochemical performance. Moreover, we give an overview of recent approaches to enhance electrical conductivity and structural stability of cathode and anode materials based on NASICON structure. We believe that this review provides a pertinent insight into relevant design principles and inspires further research in this respect.