A Novel Inorganic Polymer as Cathode Material for Secondary Lithium Batteries

Summary: This paper introduces a new inorganic poly(phosphazene disulfide) material. With unique element composition and molecular structure, the polymer has noncombustible safety and preferable conductivity. When used as cathode material for rechargeable lithium batteries, the polymer's first discharge capacity is as high as 467.9 mAh · g^?1, which can be retained at 409.9 mAh · g^?1 after 60 repeated cycles. Therefore, it has a great application potential in the field of lithium batteries.

Replacement of the Cl atoms by S? S groups by refluxing Na₂S₂ and linear poly(dichloro‐phosphazene).     

复合正极材料xLiFePO_4·yLi_3V_2(PO_4)_3/C的合成及其电化学性能

以聚吡咯(PVP K60)为表面活性剂和碳源,采用流变相法合成了x Li Fe PO4·y Li3V2(PO4)3/C正极材料样品。利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)对样品形貌和结构进行了测试;采用电池测试仪和电化学工作站对样品电化学性能进行了测试,分析了不同复合比(x:y)对其结构和电化学性能的影响。研究表明:复合材料中存在两相复合与元素掺杂两种效应;当复合比为5∶1时材料的电化学性能最优,在0.1和10 C倍率下放电容量分别达到162.7和104.6 m Ah·g-1,且具有良好的循环稳定性。     

以Mn3O4为锰源合成高性能LiMn2O4正极材料

以Mn3O4为锰源,采用固相反应法,在较低的温度(650℃)制得尖晶石LiMn2O4正极材料。采用X射线衍射(XRD)、扫描电镜(SEM)、循环伏安和恒流充放电等技术对其相组成、微结构和电化学性能进行表征。结果表明该正极材料结晶良好,一次粒径约为150 nm。它的电化学性能,尤其是循环性能,明显优越于在较高温度合成的LiMn2O4。在电流密度为74 mA?g-1时,测得比容量为128 mAh?g-1,在1 480 mA?g-1时,比容量为105 mAh?g-1;在室温、148 mA?g-1充放电200次循环后,容量保持率为93%。     

Synthesis and characterization of triclinic structural LiVPO4F as possible 4.2 V cathode materials for lithium ion batteries

A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted under an Ar atmosphere to yield VPO4. The transition-metal reduction is facilitated by the CTR based on C→CO transition. These CTR conditions favor stabilization of the vanadium as V^3＋ as well as leaving residual carbon, which is useful in the subsequent electrode processing. Secondly, VPO4 reacts with ElF to yield LiVPO4F product. The property of the LiVPO4F was investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement. XRD studies show that LiVPO4F synthesized has triclinic structure（space group p I ）, isostructural with the naturally occurring mineral tavorite, EiFePO4-OH. SEM image exhibits that the particle size is about 2μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of LiVPO4F powder is 119 mA·h/g at the rate of 0.2C with an average discharge voltage of 4.2V （vs Ei/Li^＋）, and the capacity retains 89 mA·h/g after 30 cycles.     

Si/CNTs@melamine-formaldehyde resin-based carbon composites and its improved energy storage performances

In this paper, Si/carbon nanotubes@melamine-formaldehyde resin (MFR)-based carbon (Si/CNTs@C) composites have been fabricated by surface modification, electrostatic self-assembly, cross-linking of MFR under hydrothermal treatment and further carbonization. The microstructure of the Si/CNTs@C composites was characterized, and the effects of CNTs content in Si/CNTs@C composites on their electrochemical performances were also investigated in detail. The results indicate Si/CNTs@C composites as anode materials of Li-ion batteries exhibit better high-rate and cycling performances compared to Si and Si@MFR-based carbon composites. Notably, Si/CNTs@C composites with 10.4 wt% CNTs show specific capacities of 1900, 1879, 1,688, 1,394, 1,189 mAh·g⁻¹ at 0.2, 0.5, 1, 2, and 3 A·g⁻¹, respectively. Even at 4 and 5 A·g⁻¹, their capacities still reach 970 and 752 mAh·g⁻¹, respectively. Moreover, they deliver a reversible capacity of 1,184 mAh·g⁻¹ at 0.5 A·g⁻¹ after 100 cycles. Therefore, the reasonable structure is of great significance for enhancing the electrochemical performances of Si-based composites.     

Fabrication of co-PVDF/modacrylic/SiO2 nanofibrous membrane: Composite separator for safe and high performance lithium-ion batteries

Highly porous free-standing co-poly(vinylidene fluoride)/modacrylic/SiO₂ nanofibrous membrane was developed using electrically-assisted solution blow spinning method. The performance and the potential of the membrane as a lithium-ion battery separator were investigated. The addition of modacrylic enhanced the solution spinnability that resulted in defect-free membranes. Moreover, the presence of modacrylic enhanced the dimensional and thermal stabilities, while the addition of hydrophilic SiO₂ nanoparticle enhanced both mechanical property and ionic conductivity. Combustion test results illustrated that the presence of modacrylic provide flame retarding property over a set of different polymeric-based membranes. Electrochemical performance results showed that the developed membrane can increase the battery capacity compared with the commercial separator.     

Hybrid anion exchange membranes with adjustable ion transport channels designed by compounding SEBS and homo-polystyrene

Hybrid anion exchange membranes (AEMs) were prepared via chemically functionalizing and crosslinking poly(styrene-b-[ethylene-co-butylene]-b-styrene) (SEBS) copolymers and low molecular weight homo-polystyrene (hPS). Via sequential chloromethylation, crosslinking, quaternization, and alkalization, a series of hPS/SEBS AEMs were obtained with varying content of hPS. Systematic structural, morphological, mechanical, absorption, and transport measurements reveal that these properties depend on the total PS content in the membranes. Particularly, increasing total PS content causes (a) PS domains in the AEMs transition the cylindrical morphology to lamella-like morphology with comparable correlation length; (b) Young's modulus, water uptake, swelling ratio, ionic exchange capacity and ionic conductivity of the AEMs, and T_g of PS phase increase. In addition, the alkaline stability of the hPS/SEBS AEMs is also improved by addition of hPS. These findings suggest that the proposed method can develop high performance SEBS AEMs that are suitable for fuel cell applications.     

Immobilization of multicopper oxidase from Pyrobaculum aerophilum onto an electrospun-aligned single-walled carbon nanotube surface via a carbon-nanotube-binding peptide for biocathode

Biofuel cells (BFCs) that produce electrical energy from organic resources through enzymatic reactions have been attracting significant attention. Owing to the high electrical conductivity of carbon nanotubes (CNTs), their modification on the electrode surface of a BFC is expected to increase the current, and their high specific surface area may be useful in increasing the power output. Previously, we constructed a biocathode by immobilizing multicopper oxidase from Pyrobaculum aerophilum (McoP) with a carbon nanotube binding peptide (CBP) sequence on the CNTs. This resulted in higher current densities than when using enzymes without CBP sequences. However, owing to the randomly stacked CNTs on the surface of the electrodes, their conductive properties were impaired and performance as biocathodes was poor. Herein, we constructed a biocathode in which single-walled CNTs (SWCNTs) were oriented one-dimensionally and McoP is immobilized on the surface of an SWNCT via CBP. The current density was successfully increased by two-fold by orienting the CNTs and orienting and immobilizing McoP on their surfaces. This technology provides insights into the development of biodevices with controlled orientation of both the SWCNTs and enzymes immobilized on their surfaces.     

Achieving superiorly high heat-dimensional stability,high strength,and good electrochemical performance for electrospun separators in power lithium-ion battery through building unique condensed structure based on polyimide and poly (m-phenylene isophthalamide)

It is still a challenge for simultaneously achieving high heat resistance, high strength and outstanding electrochemical performance for separators in power lithium-ion battery (PLB). Herein, new high performance electrospun separators are developed through building unique structure based on polyimide (PI) and poly (m-phenylene isophthalamide) (PMIA). Orthogonal tests (4⁴) show that the magnitude order of electrospinning factors on the morphology of membrane is concentration>injection rate>receiving distance>voltage. With the optimum factors, the electrospun membrane (PI/PMIA) was prepared, which was further pressed at 100°C for 10 min to get treated membrane (H-PI/PMIA). Interestingly, the comprehensive performance of PI/PMIA is not a simple combination of those of PI and PMIA; instead, PI/PMIA has much better thermal and mechanical properties than both PI and PMIA, proving that PI/PMIA has a synergistic effect. PI/PMIA and H-PI/PMIA not only have good ionic conductivity and electrochemical stability, but also have superiorly high properties including dimensional stability (thermal shrinkage temperature>300°C), tensile strengths (24.1 MPa for PI/PMIA, 34.3 MPa for H-PI/PMIA) and capacity retentions (97.9%, 99.2%) compared with electrospun membranes for PLBs reported in the literature so far (SCI database). The mechanism behind these attractive performances is discussed from condensed structure of membranes.     

The influence of poly(3,4-ethylenedioxythiophene) modification on the transport properties and fuel cell performance of Nafion-117 membranes

Nafion-117/PEDOT composite membranes were synthesized by in situ chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) using ammonium persulfate as an oxidant. The polymerization of EDOT in Nafion membranes for various EDOT/oxidant treatment sequences was studied for the first time. PEDOT introduction leads to a slight decrease in both the ion-exchange capacity and water uptake of the composite membranes, as well as to an increase in cationic transport. Membranes initially treated with an oxidant exhibit better conductivity and lower hydrogen permeability. The effect of both modification of Nafion-117 membranes by PEDOT and hot-pressing of hydrogen-oxygen membrane-electrode assemblies (MEAs) on the performance of proton-exchange membrane fuel cells was studied. The maximum power density of the fabricated MEAs increases 1.5-fold: from 510 (for a pristine Nafion-117 membrane) to 810 mW cm⁻² (for a membrane modified by PEDOT). The current density at a voltage of 0.4 V reaches 1248 and 2246 mA cm⁻², respectively.