碳包覆对磷酸铁锂高温循环性能的影响机理

制备了碳包覆完整和不完整的2种磷酸铁锂，用以研究碳包覆对使用广泛的磷酸铁锂/石墨电池体系高温循环性能的影响机理。X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、粉末电阻率和扣式电池等测试表明2种物料的晶体结构、颗粒尺寸、克容量等性能相近，仅碳包覆完整度差异大。将2种物料组装成磷酸铁锂/石墨软包电芯并在60℃高温下进行1C充放电循环测试，结果表明完整的碳包覆可使其在1 250次循环后的容量保持率由80.4%提升至84.9%。在此基础上，我们成功定量极化容量和热力学容量的改善幅度，可知二者占比分别为76%和24%，这说明碳包覆的主要影响机制是为磷酸铁锂正极提供完整的导电网络，进而降低极化损失。铁溶出测试结果表明，碳包覆的直接抑制作用并不明显，其主要作用可能是通过降低电芯中的水含量从而间接抑制铁溶出，并减少部分热力学容量损失。     

A Porous Mooncake-Shaped Li4Ti5O12 Anode Material Modified by SmF3 and Its Electrochemical Performance in Lithium Ion Batteries

Reasonably designing and synthesizing advanced electrode materials is significant to enhance the electrochemical performance of lithium ion batteries (LIBs). Herein, a metal–organic framework (MOF, Mil-125) was used as a precursor and template to successfully synthesize the porous mooncake-shaped Li₄Ti₅O₁₂ (LTO) anode material assembled from nanoparticles. Even more critical, SmF₃ was used to modify the prepared porous mooncake-shaped LTO material. The SmF₃-modified LTO maintained a porous mooncake-shaped structure with a large specific surface area, and the SmF₃ nanoparticles were observed to be attach on the surface of the LTO material. It has been proven that the SmF₃ modification can further facilitate the transition from Ti⁴⁺ to Ti³⁺, reduce the polarization of electrode, decrease charge transfer impedance (R_ct) and solid electrolyte interface impedance (R_sei), and increase the lithium ion diffusion coefficient (D_Li), thereby enhancing the electrochemical performance of LTO. Therefore, the porous mooncake-shaped LTO modified using 2 wt % SmF₃ displays a large specific discharge capacity of 143.8 mAh g⁻¹ with an increment of 79.16 % compared to pure LTO at a high rate of 10 C (1 C=170 mAh g⁻¹), and shows a high retention rate of 96.4 % after 500 cycles at 5 C-rate.     

卤素化学中的铈

卤素化学是聚合物工业生产中的重要组成部分,作为一种有吸引力的策略,它在活化天然气中轻链烷烃方面越来越受到重视.CeO2基催化剂在卤化氢回收方面有着令人兴奋的潜力,这使得基于卤素的小分子活化过程具有高效率.本文综述了近年来在高分子工业(聚氯乙烯、聚氨酯和聚碳酸酯)和天然气改质中轻烃活化方面应用的铈基催化剂的研究进展,讨论了铈催化剂的作用机理和面临的挑战,以期为未来催化材料的设计和应用提供帮助.     

Application of flow chemistry to the reduction of nitriles to aldehydes

Reduction of nitriles to aldehydes with diisobutylaluminium hydride (DIBAL-H) is an important transformation in organic chemistry. But the use of this reaction is limited for the lack of reproducibility due to the instability of the intermediates formed. In the current article we disclose the improvement of the reaction applying continuous flow technology.     

Surfactant-Mediated and Morphology-Controlled Nanostructured LiFePO4/Carbon Composite as a Promising Cathode Material for Li-Ion Batteries

The synthesis of morphology-controlled carbon-coated nanostructured LiFePO₄ (LFP/Carbon) cathode materials by surfactant-assisted hydrothermal method using block copolymers is reported. The resulting nanocrystalline high surface area materials were coated with carbon and designated as LFP/C123 and LFP/C311. All the materials were systematically characterized by various analytical, spectroscopic and imaging techniques. The reverse structure of the surfactant Pluronic® 31R1 (PPO-PEO-PPO) in comparison to Pluronic® P123 (PEO-PPO-PEO) played a vital role in controlling the particle size and morphology which in turn ameliorate the electrochemical performance in terms of reversible specific capacity (163 mAh g⁻¹ and 140 mAh g⁻¹ at 0.1 C for LFP/C311 and LFP/C123, respectively). In addition, LFP/C311 demonstrated excellent electrochemical performance including lower charge transfer resistance (146.3 Ω) and excellent cycling stability (95 % capacity retention at 1 C after 100 cycles) and high rate capability (163.2 mAh g⁻¹ at 0.1 C; 147.1 mAh g⁻¹ at 1 C). The better performance of the former is attributed to LFP nanoparticles (<50 nm) with a specific spindle-shaped morphology. Further, we have also evaluated the electrode performance with the use of both PVDF and CMC binders employed for the electrode fabrication.     

LiNi0.8Co0.15Al0.05O2正极材料的FePO4包覆改性

使用液相包覆工艺对LiNi_(0.8)Co_(0.15)Al_(0.05)O_2(NCA)材料进行FePO_4包覆改性,利用FePO_4优异的结构稳定性与热稳定性,对NCA的长期可靠性与安全性能进行改良。重点研究FePO_4包覆对NCA材料的改性效果,以及不同包覆量造成的NCA材料电化学性能差异。表面包覆的FePO_4保护层,能够防止NCA材料与电解液直接接触发生副反应,抑制长期循环过程中过渡金属离子的溶出,保持结构的长期稳定性。当包覆量为1.0%(w/w)时,NCA材料表现出最优的综合性能,充放电循环800次后,容量保持率依然高达95%,25℃下存储100 d后,容量保持率也高于95%,达到了兼顾能量密度、使用寿命及安全性能的理想效果。     

Creation and control of quasi-two dimensional electron gas at yttrium aluminum oxides/strontium titanate heterointerfaces by spin coating

Despite of extensive researches about oxide heterointerfaces, preparing method and intrinsic mechanism are all challenging topics. Here, we generate a series of stable quasi two dimensional electron gases (q-2DEGs) at yttrium aluminum oxides/strontium titanate (YAO/STO) heterointerfaces by the spin coating for the first time. It is found that the thickness and the stoichiometry ratio are the key factors for the creation of q-2DEG, which is formed under the premise of thickness (about 81.1 ∼ 356.4 nm) and the rich-Al (Al:Y≥1:1). The underlying mechanism can be attributed to oxygen vacancies derived from the redox reaction between YAO film and STO substrate. In addition, the conductive behavior can be modulated by the light illumination and the value of photoinduced change reaches 153.7% at low temperature. This work paves a novel way to fabricate 2DEG massively and helpful for a deep understanding about the conductive mechanism of oxide heterostructures.     

Order parameter saturation (plateau effect) as a function of composition in the sanmartinite (ZnWO4)-Cuproscheelite (CuWO4) solid solution

Metallic nanoparticles are deposited on multilayers of an unsaturated phospholipid to form a planar nano-composite material. At temperatures near or above the main transition of the lipid, the organic layers exhibit a high degree of mobility and allow for a significant rearrangement of the metallic particles. Originally after deposition, the inter-particle distances correspond to the average bilayer thickness of the given phospholipid. After annealing of the composite structure in the presence of moisture, the spacing between the particles is significantly reduced, associated with an interdigitation of aliphatic chains in the hydrophobic region. This phenomenon is still observed after UV irradiation of the unsaturated hydrocarbon chains.     

Crosslinked PDMS elastomers and coatings from the thermal curing of vinyl‐functionalized PDMS and a diazide aliphatic crosslinker

The crosslinking of poly(dimethylsiloxane) elastomers and coatings by the thermal curing of poly(dimethylsiloxane‐co‐methylvinylsiloxane) and 1,12‐diazido‐dodecane was studied. This crosslinking pathway relies on the cycloaddition of azides and alkenes as well as the thermal generation of nitrene transient radicals, which react with alkenes, yielding respectively 1,2,3‐triazoline and aziridine crosslinking knots. The influence of temperature and the ratio of azide and vinyl functionalities has been investigated by rheological, swelling, and insoluble fraction measurements for materials crosslinked in bulk and by comparison of the thickness before and after extraction of the soluble materials by soxhlet extraction for the crosslinked coatings. The preparation of highly crosslinked PDMS‐based elastomers and coatings has been demonstrated, even if the fraction of elastically effective crosslinks in bulk remained below 160 mol/m³. Advantageously, this system does not require additional initiator or catalyst, is not sensitive to moisture or oxygen, and can be extended to a wide range of unsaturated polymers as well as different organic or inorganic solid substrates. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The effect of basecoat pigmentation on mechanical properties of an automotive basecoat/clearcoat system during weathering

The aim of this study is to elucidate the effect of basecoat pigmentation on mechanical aspects of an automotive basecoat/clearcoat (BC/CC) system during artificial weathering exposures. A silver basecoat as the most reflective and a black basecoat as the most absorptive basecoat were selected. These two extreme behaviored basecoats were chosen with hopes that other basecoats would behave somewhere between the silver and the black extremes. The structural and mechanical properties of the coatings were investigated after various weathering exposure times (0, 150, 300, 450, 600 h). Dynamic mechanical thermal analysis (DMTA) was carried out to study variations in structure and basic characteristics of the system such as cross-linking density and T_g during weathering. In order to investigate variations in mechanical properties of the system, nano indentation, nano scratch, and tensile tests were also utilized.It was found that although both silver and black systems experienced post-curing reactions (dominant at earlier stages of weathering) and degradation reactions (dominant at later stages of weathering), but basecoat pigmentation affected the post-curing and degradation reaction rates of the BC/CC system, leading to variations in mechanical properties. It was concluded that post-curing occurred to a greater extent in the black pigmented system whilst in the silver pigmented system weathering degradation was much more sever.