Shiyou Zheng

Electrospun Sb/C Fibers for a Stable and Fast Sodium-Ion Battery Anode

Sodium-ion batteries (SIBs) are considered a top alternative to lithium-ion batteries (LIBs) for large-scale renewable energy storage units due to their low cost and the abundance of sodium-bearing precursors in the earths mineral deposits. However, the development of anode materials for SIBs to date has been mainly limited to carbonaceous materials with minimal research devoted to high capacity alloy-based materials. In this study, an antimony (Sb)/carbon (C) electrode with ~30 nm Sb nanoparticles (NPs) uniformly encapsulated in interconnecting one-dimensional (1D) 400 nm carbon fibers (denoted as SbNP@C) was fabricated using a simple and scalable electrospinning method. This binder-free, current collector-free SbNP@C electrode demonstrated high capacity and stable long-term cycling performance at various current densities. The SbNP@C electrode showed an initial total capacity of 422 mAh/gelectrode and retained 350 mAh/gelectrode after 300 deep charge-discharge cycles under 100 mA/gSb. Moreover, because of the efficient 1D sodium-ion transport pathway and the highly conductive network of SbNP@C, the electrode preserved high overall capacities even when cycled at high currents, extending its usability to high power applications.

Selenium@Mesoporous Carbon Composite with Superior Lithium and Sodium Storage Capacity

Selenium-impregnated carbon composites were synthesized by infusing Se into mesoporous carbon at a temperature of 600 °C under vacuum. Ring-structured Se8 was produced and confined in the mesoporous carbon, which acts as an electronic conductive matrix. During the electrochemical process in low-cost LiPF6/EC/DEC electrolyte, low-order polyselenide intermediates formed and were stabilized by mesoporous carbon, which avoided the shuttle reaction of polyselenides. Exceptional electrochemical performance of Se/mesoporous carbon composites was demonstrated in both Li-ion and Na-ion batteries. In lithium-ion batteries, Se8/mesoporous carbon composite cathodes delivered a reversible capacity of 480 mAh g(-1) for 1000 charge/discharge cycles without any capacity loss, while in Na-ion batteries, it provided initial capacity of 485 mAh g(-1) and retained 340 mAh g(-1) after 380 cycles. The Se8/mesoporous carbon composites also showed excellent rate capability. As the current density increased from 0.1 to 5 C, the capacity retained about 46% in Li-ion batteries and 34% in Na-ion batteries.

In Situ Formed Lithium Sulfide/Microporous Carbon Cathodes for Lithium-Ion Batteries

Highly stable sulfur/microporous carbon (S/MC) composites are prepared by vacuum infusion of sulfur vapor into microporous carbon at 600 °C, and lithium sulfide/microporous carbon (Li2S/MC) cathodes are fabricated via a novel and facile in situ lithiation strategy, i.e., spraying commercial stabilized lithium metal powder (SLMP) onto a prepared S/MC film cathode prior to the routine compressing process in cell assembly. The in situ formed Li2S/MC film cathode shows high Coulombic efficiency and long cycling stability in a conventional commercial Li-ion battery electrolyte (1.0 M LiPF6 + EC/DEC (1:1 v/v)). The reversible capacities of Li2S/MC cathodes remain about 650 mAh/g even after 900 charge/discharge cycles, and the Coulombic efficiency is close to 100% at a current density of 0.1C, which demonstrates the best electrochemical performance of Li2S/MC cathodes reported to date. Furthermore, this Li2S/MC film cathode fabricated via our in situ lithiation strategy can be coupled with a Li-free anode, such as graphite, carbon/tin alloys, or Si nanowires to form a rechargeable Li-ion cell. As the Li2S/MC cathode is paired with a commercial graphite anode, the full cell of Li2S/MC-graphite (Li2S-G) shows a stable capacity of around 600 mAh/g in 150 cycles. The Li2S/MC cathodes prepared by high-temperate sulfur infusion and SLMP prelithiation before cell assembly are ready to fit into current Li-ion batteries manufacturing processes and will pave the way to commercialize low-cost Li2S-G Li-ion batteries.

High Performance C/S Composite Cathodes with Conventional Carbonate-Based Electrolytes in Li-S Battery

High stable C/S composites are fabricated by a novel high-temperature sulfur infusion into micro-mesoporous carbon method following with solvent cleaning treatment. The C/S composite cathodes show high Coulombic efficiency, long cycling stability and good rate capability in the electrolyte of 1.0 M LiPF6 + EC/DEC (1:1 v/v), for instance, the reversible capacity of the treated C/S-50 (50% S) cathode retains around 860 mAh/g even after 500 cycles and the Coulombic efficiency is close to 100%, which demonstrates the best electrochemical performance of carbon-sulfur composite cathodes using the carbonate-based electrolyte reported to date. It is believed that the chemical bond of C-S is responsible for the superior electrochemical properties in Li-S battery, that is, the strong interaction between S and carbon matrix significantly improves the conductivity of S, effectively buffers the structural strain/stress caused by the large volume change during lithiation/delithiation, completely eliminates the formation of high-order polysulfide intermediates, and substantially avoids the shuttle reaction and the side reaction between polysulfide anions and carbonate solvent, and thus enables the C/S cathode to use conventional carbonate-based electrolytes and achieve outstanding electrochemical properties in Li-S battery. The results may substantially contribute to the progress of the Li-S battery technology.

Three-Dimensional Graphene/Single-Walled Carbon Nanotube Aerogel Anchored with SnO2 Nanoparticles for High Performance Lithium Storage

A unique 3D graphene-single walled carbon nanotube (G-SWNT) aerogel anchored with SnO2 nanoparticles (SnO2@G-SWCNT) is fabricated by the hydrothermal self-assembly process. The influences of mass ratio of SWCNT to graphene on structure and electrochemical properties of SnO2@G-SWCNT are investigated systematically. The SnO2@G-SWCNT composites show excellent electrochemical performance in Li-ion batteries; for instance, at a current density of 100 mA g-1, a specific capacity of 758 mAh g-1 was obtained for the SnO2@G-SWCNT with 50% SWCNT in G-SWCNT and the Coulombic efficiency is close to 100% after 200 cycles; even at current density of 1 A g-1, it can still maintain a stable specific capacity of 537 mAh g-1 after 300 cycles. It is believed that the 3D G-SWNT architecture provides a flexible conductive matrix for loading the SnO2, facilitating the electronic and ionic transportation and mitigating the volume variation of the SnO2 during lithiation/delithiation. This work also provides a facile and reasonable strategy to solve the pulverization and agglomeration problem of other transition metal oxides as electrode materials.

Flexible Overoxidized Polypyrrole Films with Orderly Structure as High-Performance Anodes for Li- and Na-Ion Batteries

Flexible polypyrrole (PPy) films with highly ordered structures were fabricated by a novel vapor phase polymerization (VPP) process and used as the anode material in lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). The PPy films demonstrate excellent rate performance and cycling stability. At a charge/discharge rate of 1 C, the reversible capacities of the PPy film anode reach 284.9 and 177.4 mAh g-1 in LIBs and SIBs, respectively. Even at a charge/discharge rate of 20 C, the reversible capacity of the PPy film anode retains 54.0% and 52.9% of the capacity of 1 C in LIBs and SIBs, respectively. After 1000 electrochemical cycles at a rate of 10 C, there is no obvious capacity fading. The molecular structure and electrochemical behaviors of Li- and Na-ion doping and dedoping in the PPy films are investigated by XPS and ex situ XRD. It is believed that the PPy film electrodes in the overoxidized state can be reversibly charged and discharged through the doping and dedoping of lithium or sodium ions. Because of the self-adaptation of the doped ions, the ordered pyrrolic chain structure can realize a fast charge/discharge process. This result may substantially contribute to the progress of research into flexible polymer electrodes in various types of batteries.

Red Phosphorus Embedded Cross Link Structural Carbon Films as Flexible Anodes for Highly Reversible Li-Ion Storage

Red phosphorus (P) is considered to be one of the most attractive anodic materials for lithium-ion batteries (LIBs) due to its high theoretical capacity of 2596 mAh g-1. However, intrinsic characteristics such as the poor electronic conductivity and large volume expansion at lithiation impede the development of red P. Here, we design a new strategy to embed red P particles into a cross-link-structural carbon film (P-C film), in order to improve the electronic conductivity and accommodate the volume expansion. The red P/carbon film is synthesized via vapor phase polymerization (VPP) followed by the pyrolysis process, working as a flexible binder-free anode for LIBs. High cycle stability and good rate capability are achieved by the P-C film anode. With 21% P content in the film, it displays a capacity of 903 mAh g-1 after 640 cycles at a current density of 100 mA g-1 and a capacity of 460 mAh g-1 after 1000 cycles at 2.0 A g-1. Additionally, the Coulombic efficiency reaches almost 100% for each cycle. The superior properties of the P-C films together with their facile fabrication make this material attractive for further flexible and high energy density LIB applications.

Sulfur encapsulated in thermally reduced graphite oxide as a cathode for Li–S batteries

Rechargeable Li–S batteries are receiving ever-increasing attention due to their high theoretical energy density and inexpensive raw sulfur materials. However, their practical applications have been hindered by short cycle life and limited power density owing to the poor electronic conductivity of sulfur species, diffusion of soluble polysulfide intermediates (Li2Sn, n = 4–8) and the large volume change of the S cathode during charge/discharge. Optimizing the carbon framework is considered as an effective approach for constructing high performance S/carbon cathodes because the microstructure of the carbon host plays an important role in stabilizing S and restricting the “shuttle reaction” of polysulfides in Li–S batteries. In this work, reduced graphite oxide (rGO) materials with different oxidation degree were investigated as the matrix to load the active material by an in situ thermally reducing graphite oxide (GO) and intercalation strategy under vacuum at 600 °C. It has been found that the loaded amount of S embedded in the rGO layer for the S/carbon cathode and its electrochemical performance strongly depended on the oxidation degree of GO. In particular, on undergoing CS2 treatment, the rGO–S cathode exhibits extraordinary performances in Li–S batteries. For instance, at a current density of 0.2 A g−1, the optimized rGO–S cathode shows a columbic efficiency close to 100% and retains a capacity of around 750 mA h g−1 with progressive cycling up to over 250 cycles.

Molecular self-assembly of a nanorod N-Li4Ti5O12/TiO2/C anode for superior lithium ion storage

Spinel lithium titanate (Li4Ti5O12, LTO) is one of the most appealing anode materials for lithium-ion batteries (LIBs) due to its long cycle life and high safety performance. However, its low intrinsic electronic conductivity limits its high rate capability. Herein, we develop a novel one-pot in situ molecular self-assembly approach to prepare a dual N- and anatase-TiO2- modified Li4Ti5O12/C nanorod material (NT-LTO/C). Polypyrrole (PPy), as a pivotal carbon and nitrogen source, is introduced to confine the morphology and particle size of the NT-LTO/C anode. Due to the synergistic effects of the multilevel particle structure, uniform carbon coating, N doping, anatase TiO2 pseudopotential effect and such benefits, the NT-LTO/C electrode delivers a high reversible capacity of 196.3 mA h g−1 at 0.5C, and it maintains 105.5 mA h g−1 even at an ultrahigh rate of 100C with progressive cycling of more than 3000 cycles. In addition, the three electrode pouch full-cell shows much smaller polarization than the pristine one. This novel and facile molecular self-assembly method has broad advanced functional material applications including for ceramics, polymer/carbon-based metal alloys and inorganic non-metallic materials.

Ultrafine Red P Nanoconfined between Expanded Graphene Sheets for High-Performance Lithium-ion Batteries

A novel and facile strategy is proposed to synthesize red P nanoconfined between expanded graphene sheets (P@expanded-G) as an anode material for lithium-ion batteries by oxidation-assembly-reduction, followed by a high-temperature infiltration method. It is found that an appropriate interlaminar distance of graphene sheets, which is achieved by tailoring the mass ratio of graphene and carbon nanotubes, can ensure high loading content and effective nanoconfinement of red P simultaneously, resulting in high electrochemical performances for the P@expanded-G samples. For instance, the optimized P@expanded-G50 anode exhibits a specific capacity as high as 1010 mA h g−1 based on the total mass (2053 mA h g−1 based on the red P mass) with a coulombic efficiency close to 100% after 500 cycles at 0.1 A g−1. Moreover, as the current density increases to 2.0 A g−1, the specific capacity still remains over 440 mA h g−1 (based on the total mass) with progressive cycling up to more than 2000 cycles. Structural characterization reveals that the existence of a large amount of uniformly nanoconfined red P between the expanded graphene sheets and the formation of P–C and P–O bonds are mainly responsible for the much improved electrochemical performances.