Zhizhong Xie

Advanced Separators for Lithium‐Ion and Lithium–Sulfur Batteries: A Review of Recent Progress

Li-ion and Li-S batteries find enormous applications in different fields, such as electric vehicles and portable electronics. A separator is an indispensable part of the battery design, which functions as a physical barrier for the electrode as well as an electrolyte reservoir for ionic transport. The properties of the separators directly influence the performance of the batteries. Traditional polyolefin separators showed low thermal stability, poor wettability toward the electrolyte, and inadequate barrier properties to polysulfides. To improve the performance and durability of Li-ion and Li-S batteries, development of advanced separators is required. In this review, we summarize recent progress on the fabrication and application of novel separators, including the functionalized polyolefin separator, polymeric separator, and ceramic separator, for Li-ion and Li-S batteries. The characteristics, advantages, and limitations of these separators are discussed. A brief outlook for the future directions of the research in the separators is also provided.

Hydrogen Ion Supercapacitor: A New Hybrid Configuration of Highly Dispersed MnO2 in Porous Carbon Coupled with Nitrogen-Doped Highly Ordered Mesoporous Carbon with Enhanced H-Insertion

A new configuration of hydrogen ion supercapacitors was reported. A positive electrode composed of pseudocapacitive MnO2, highly dispersed into active porous carbon through an impregnation method, was combined with a nitrogen-doped highly ordered mesoporous carbon with enhanced electrochemical hydrogen insertion capacity as a negative electrode. During the operation, hydrogen ion shuttled between MnO2 and carbon electrodes. The MnO2 was formed on the surface of nanostructured carbon through a spontaneous redox reaction. Operating in an aqueous neutral solution, the hybrid device demonstrated an extended working voltage to ∼2.1 V with good cycle life.

Self-assembly synthesis of a unique stable cocoon-like hematite @C nanoparticle and its application in lithium ion batteries

A novel cocoon-like Fe2O3@C nanoparticle was fabricated via a facile hydrothermally molecular self-assembly procedure. Compared to bare Fe2O3 nanoparticles, the carbon coated Fe2O3 nanoparticles exhibit higher specific capacity, excellent rate capacity and cyclic stability as the anode in lithium ion batteries. These cocoon-like Fe2O3@C nanoparticles carry enhanced lithium storage properties with a reversible capacity of 358mAhg-1 after 150 cycles under the current density of 1000mAg-1, while the carbon-free bare Fe2O3 can only deliver a much lower capacity of 127.6mAhg-1 with a continuously decreasing trend. The excellent performance of Fe2O3@C is attributed to the coated carbon layers, which not only enhance the electronic conductivity but also reduce the stress upon the Fe2O3 nanoparticles caused by the volume change during the charge/discharge process.

High-Capacity and Self-Stabilized Manganese Carbonate Microspheres as Anode Material for Lithium-Ion Batteries

Manganese carbonate (MnCO3) is an attractive anode material with high capacity based on conversion reaction for lithium-ion batteries (LIBs), but its application is mainly hindered by poor cycling performance. Building nanostructures/porous structures and nanocomposites has been demonstrated as an effective strategy to buffer the volume changes and maintain the electrode integrity for long-term cycling. It is widely believed that microsized MnCO3 is not suitable for use as anode material for LIBs because of its poor conductivity and the absence of nanostructure. Herein, different from previous reports, spherical MnCO3 with the mean diameters of 6.9 μm (MnCO3-B), 4.0 μm (MnCO3-M), and 2.6 μm (MnCO3-S) were prepared via controllable precipitation and utilized as anode materials for LIBs. It is interesting that the as-prepared MnCO3 microspheres demonstrate both high capacity and excellent cycling performance comparable to their reported nanosized counterparts. MnCO3-B, MnCO3-M, and MnCO3-S deliver reversible specific capacities of 487.3, 573.9, and 656.8 mA h g(-1) after 100 cycles, respectively. All the MnCO3 microspheres show capacity retention more than 90% after the initial stage. The advantages of MnCO3 microspheres were investigated via constant-current charge/discharge, cyclic voltammetry and electrochemical impedance spectroscopy. The results indicate that there should be substantial structure transformation from microsized particle to self-stabilized nanostructured matrix for MnCO3 at the initial charge/discharge stage. The evolution of EIS during charge/discharge clearly indicates the formation and stabilization of the nanostructured matrix. The self-stabilized porous matrix maintains the electrode structure to deliver excellent cycling performance, and contributes extra capacity beyond conversion reaction.

Highly ordered 3D macroporous scaffold supported Pt/C oxygen electrodes with superior gas-proton transportation properties and activities for fuel cells

An oxygen electrode finds many applications in various electrochemical energy conversion devices such as fuel cells and metal–air batteries. Highly efficient gas–proton transportation at the electrode is very important to enhance the power density of these devices. Herein, we report the construction of a highly efficient oxygen electrode with substantially improved proton conductivity and gas transportation properties using three dimensionally ordered macroporous Nafion/Cs2.5H0.5PW12O40, 3DOM Nafion/CsHPW, scaffold supported Pt/C nanocomposites. The best results were obtained for cells with 3DOM Nafion/CsHPW with 10% CsHPW, achieving a maximum power density of 955 mW cm−2, 31% higher than 730 mW cm−2 for the cell with the conventional Nafion-binder based oxygen electrode. The proton conductivity of the 10% 3DOM Nafion/CsHPW catalyst layer is 1.56 × 10−2 S cm−1, 112% higher than 7.35 × 10−3 S cm−1 measured for the conventional catalyst layer with the Nafion binder. The results demonstrate the significant advantages of the oxygen electrodes with the Pt/C-3DOM Nafion/CsHPW architecture over the conventional Nafion-binder based ones, with the significantly enhanced proton conductivity of uniformly distributed CsHPW nanoparticles (NPs) and much better gas diffusion properties of the 3DOM architecture.

Electrochemical Hydrogen Storage in a Highly Ordered Mesoporous Carbon

A highly order mesoporous carbon has been synthesized through a strongly acidic, aqueous cooperative assembly route. The structure and morphology of the carbon material were investigated using TEM, SEM and nitrogen adsorption-desorption isotherms. The carbon was proven to be meso-structural and consisted of graphitic micro-domain with larger interlayer space. AC impedance and electrochemical measurements reveal that the synthesized highly ordered mesoporous carbon exhibits a promoted electrochemical hydrogen insertion process and improved capacitance and hydrogen storage stability. The meso-structure and enlarged interlayer distance within the highly ordered mesoporous carbon are suggested as possible causes for the enhancement in hydrogen storage. Both hydrogen capacity in the carbon and mass diffusion within the matrix were improved.

The effects of structural properties on the lithium storage behavior of mesoporous TiO2

Understanding the effects of structural properties on the lithium storage behavior of mesoporous TiO2 is crucial for further optimizing its performance through rational structure design. To achieve this, herein, the surface area and the grain size of the prepared mesoporous TiO2 are intentionally adjusted by controlling the calcination temperatures. It is found that the capacities of the mesoporous TiO2 contain both the lithium-ion insertion into the bulk phase (Q in) and the additional surface lithium storage (Q as). The Q in gradually increases with grain sizes to a steady level and then slightly drops. By contrast, the Q as is directly proportional to the specific surface area of the mesoporous TiO2 and is ascribed to the capacity originated from the lithium-ion insertion into the surface layer. The experimental comparison and analysis demonstrate that the fast kinetics of the Q as ensure both the better rate performance and capacity retention of mesoporous TiO2 than bulk ones. Specially, the mesoporous TiO2 calcinated at 350 °C shows the highest reversible specific capacity of 250.2 mA h g-1, the best rate capability (132.5 mA h g-1 at 2C) and good cycling stability. Our findings shed great light on the design of high-performance nanostructured TiO2 with surface lithium storage.

Confining nano-sized platinum in nitrogen doped ordered mesoporous carbon: An effective approach toward efficient and robust hydrogen evolution electrocatalyst

Despite recent progress in the development of earth abundant electrochemical catalyst for hydrogen evolution reaction (HER), Pt based materials still stand as the state of the art HER catalyst. Due to the high cost of Pt, it is desirable to increase the utilization efficiency of Pt in practical HER process to a realize cost effective hydrogen production. Herein, we repot a novel nitrogen doped ordered mesoporous carbon supported Pt (Pt@NOMC-A) catalyst with a low Pt loading of 7.2 wt% and show that the synergy between Pt nanoparticles and carbon support, as well as the physical confinement offered by the carbon support enhance the electrochemical performance of the novel catalyst. Pt@NOMC-A exhibits a low HER overpotential comparable with commercial 20 wt% Pt/C catalyst under acidic, neutral and alkaline condition. Furthermore, Pt@NOMC-A shows a superior electrochemical stability under working conditions suppressing that of commercial Pt/C catalyst.

Electrochemical Hydrogen Storage in Facile Synthesized Co@N-Doped Carbon Nanoparticle Composites

A Co@nitrogen-doped carbon nanoparticle composite was synthesized via a facile molecular self-assembling procedure. The material was used as the host for the electrochemical storage of hydrogen. The hydrogen storage capacity of the material was over 300 mAh g-1 at a rate of 100 mAg-1. It also exhibited superior stability for storage of hydrogen, high rate capability, and good cyclic life. Hybridizing metallic cobalt nanoparticle with nitrogen-doped mesoporous carbon is found to be a good approach for the electrochemical storage of hydrogen.

Controllable preparation and superior rate performance of spinel LiMn2O4 hollow microspheres as cathode material for lithium-ion batteries

Spinel LiMn2O4 microspheres and hollow microspheres with adjustable wall thickness have been prepared using controllable oxidation of MnCO3 microspheres precursors and following solid reactions with lithium salts. Scanning electron microscopy (SEM) investigations demonstrate that the microsphere morphology and hollow structure of precursors are inherited. The effect of hollow structure properties of as-prepared LiMn2O4 on their performance as cathode materials for lithium-ion batteries has been studied. Electrochemical performance tests show that LiMn2O4 hollow microspheres with small wall thickness exhibit both superior rate capability and better cycle performance than LiMn2O4 solid microspheres and LiMn2O4 hollow microspheres with thick wall. The LiMn2O4 hollow microspheres with thin wall have discharge capacity of 132.7 mA·h·g-1 at C/10 (14.8 mA·g-1) in the first cycle, 94.1% capacity retention at C/10 after 40 cycles and discharge capacity of 116.5 mAh·g-1 at a high rate of 5C. The apparent lithium-ion diffusion coefficient (Dapp) of as-prepared LiMn2O4 determined by capacity intermittent titration technique (CITT) varies from 10-11 to 10-8.5 cm2·s-1 showing a regular “W” shape curve plotted with test voltages. The Dapp of LiMn2O4 hollow microspheres with thin wall has the largest value among all the prepared samples. Both the superior rate capability and cycle stability of LiMn2O4 hollow microspheres with thin wall can be ascribed to the facile ion diffusion in the hollow structures and the robust of hollow structures during repeated cycling.