用纳米羟基磷灰石@多孔碳构建锂硫电池高效反应界面

由于正极活性物质硫具有能量密度高、成本低廉和储量丰富等优点,锂硫(Li-S)电池受到了人们的极大关注。然而,锂硫电池充放电过程中产生的多硫化锂的“穿梭效应”严重阻碍了其实用化进程。为了解决这个问题,本研究借助动物软骨的组成和结构特点,制备了纳米羟基磷灰石@多孔碳(nano-HA@CCPC)复合材料,并以此设计了面向正极的锂硫电池隔膜涂层。研究表明,纳米羟基磷灰石不仅对多硫化物具有吸附固定作用,并且对多硫化锂的转化具有催化作用,加快了多硫化锂的氧化还原动力学,有效地提升了活性物质硫的利用率。另外,软骨基碳复合材料的多孔结构形成了很好的导电网络,为电化学反应提供了优良的电子传导路径;也有利于电解液的浸润,加快了离子传输;碳的氮原子掺杂进一步限制了多硫化物的穿梭效应。因此,采用nano-HA@CCPC隔膜涂层的锂硫电池表现出较长的循环寿命、低的容量损失以及高的倍率性能。在0.5 C下,循环325次后,电池仍然能保持815 m Ah·g^(-1)的放电比容量,并且每次的容量衰减率仅为0.051%。nano-HA@CCPC的设计制备将为锂硫电池的发展提供新材料。

A novel permselective organo-polysulfides/PVDF gel polymer electrolyte enables stable lithium anode for lithium–sulfur batteries

Lithium-sulfur(Li-S)battery can satisfy the need of the future power battery market because of its high energy density,but the hidden dangers caused by lithium anode have seriously hindered their commercialization.Herein,an innovative gel polymer electrolyte(GPE)composed of polyvinylidene fluoride(PVDF)and organo-polysulfide polymer(PSPEG)is proposed,which could be used in semisolid-state Li-S batteries for protection of Li anodes.Particularly,organo-polysulfide polymer could chemically/electrochemically generate both inorganic and organic components simultaneously in-situ once contacting fresh Li metal surface and/or during discharging processes.And these inorganic/organic components could participate in the formation of the SEI layer and finally constitute a stable and flexible hybrid SEI layer on the surface of Li metal anode.Moreover,the organic components were permselective to lithium ions against anions.Therefore,PVDF/PSPEG GPE ensures the ideal chemical and electrochemical properties for Li-S batteries.Our work demonstrates an effective solution to solve the problems about Li anodes and contributes to the development of the safe Li metal batteries.

锂硫电池用高度环化硫化聚丙烯腈的制备

硫化聚丙烯腈因其不溶解机制和有效缓解锂硫电池中多硫化物“穿梭效应”,被认为是具有吸引力的锂硫电池正极候选材料。硫化聚丙烯腈的导电聚合物骨架具有优异的电子导电性,同时共轭主链能有效解决充放电过程中硫正极体积变化引起的正极结构坍塌问题。因硫化聚丙烯腈的固-固反应机理,有效克服了传统硫正极在醚类电解液中多硫化物溶解及穿梭效应的问题,具有高正极活性物质利用率、出色的循环稳定性和结构稳定性等优势。有许多研究工作致力于通过硫化促进剂来提高硫化聚丙烯腈的硫含量,进而提高材料的能量密度。其中,硫化聚丙烯腈主链的环化度与循环稳定性的关系引起了我们的关注。在该研究工作中,通过在硫化过程中引入无水硫酸铜和正乙基正苯基二硫代氨基甲酸锌(ZDB)合成了SPAN-C-V复合材料。无水硫酸铜和ZDB的共同引入降低了聚丙烯腈环化反应的起始温度,同时提高了产物SPAN-C-V内碳碳双键的含量,在提高了材料硫含量的同时提高了其环化度。以SPAN-C-V为正极活性物质所组装的锂硫电池展现出良好的循环稳定性和倍率性能:在0.2 C(1 C=600 mAh·kg^(-1))下循环100次后的可逆容量为601 mAh·kg^(-1),容量保持率为93%。该工作对于硫化聚丙烯腈材料的发展提供了参考。

P(VDF-HFP)-poly(sulfur-1,3-diisopropenylbenzene) functional polymer electrolyte for lithium–sulfur batteries

Lithium–sulfur(Li–S)battery as a high-energy density electrochemical energy storage system has attracted many researchers’attention.However,the shuttle effect of Li–S batteries and the challenges associated with lithium metal anode caused poor cycle performance.In this work,the organosulfide poly(sulfur-1,3-diisopropenylbenzene)(PSD)was prepared as cathode material and additive of P(VDFHFP)polymer electrolyte(P(VDF-HFP)).It was verified that P(VDF-HFP)polymer electrolyte with 10%PSD(P(VDF-HFP)-10%PSD)showed a higher ionic conductivities than that of liquid electrolyte up to2.27×10-3 S cm-1 at room temperature.The quasi-solid-state Li-S batteries fabricated with organosulfide cathode material PSD and P(VDF-HFP)based functional polymer electrolyte delivered good cycling stability(780 m Ah g-1 after 200 th cycle at 0.1 C)and rate performance(613 m Ah g-1 at 1 C).The good cycling performance could be attributed to the synergistic effect of components,including the interaction between polysulfides and polymer main chain in the organosulfide cathode,the sustained organic/inorganic hybrid stable SEI layer formed by polymer electrolyte additive PSD,the improved cathode/electrolyte interface and the good affinity between P(VDF-HFP)based functional polymer electrolyte and Li metal surface.This strategy herein may provide a new route to fabricate high-performance Li–S batteries through the organosulfide cathode and functional polymer electrolyte.

Chaos generation by a hybrid integrated chaotic semiconductor laser

We design a hybrid integrated chaotic semiconductor laser with short-cavity optical feedback.It can be assembled in a commercial butterfly shell with just three micro-lenses.One of them is coated by a transflective film to provide the optical feedback for chaos generation while insuring regular laser transmission.We prove the feasibility of the chaos generation in this compact structure and provide critical external parameters for the fabrication by theoretical simulations.Rather than the usual changeless internal parameters used in previous simulation research,we extract the real parameters of the chip by experiment.Moreover,the maps of the largest Lyapunov exponent with varying bias current and feedback intensity Kap demonstrate the dynamic characteristics under different external-cavity conditions.Each laser chip has its own optimal external cavity length(L)and feedback intensity(Kap)to generate chaos because of the different internal parameters.We have acquired two ranges of optimal parameters(L=4 mm,0.12〈Kap〈0.2 and L=5 mm,0.07〈Kap〈0.12)for two different chips.

Trapped Bose–Einstein condensates with quadrupole–quadrupole interactions

We numerically investigate the ground-state properties of a trapped Bose–Einstein condensate with quadrupole–quadrupole interaction.We quantitatively characterize the deformations of the condensate induced by the quadrupolar interaction.We also map out the stability diagram of the condensates and explore the trap geometry dependence of the stability.

Sensitivity to external optical feedback of circular-side hexagonal resonator microcavity laser

The sensitivity to fault reflection is very important for larger dynamic range in fiber fault detection technique.Using time delay signature(TDS)of chaotic laser formed by optical feedback can solve the sensitivity limitation of photodetector in fiber fault detection.The TDS corresponds to the feedback position and the fault reflection can be detected by the laser diode.The sensitivity to feedback level of circular-side hexagonal resonator(CSHR)microcavity laser is numerically simulated and the feedback level boundaries of each output dynamic state are demonstrated.The peak level of TDS is utilized to analyze the sensitivity.The demonstration is presented in two aspects:the minimum feedback level when the TDS emerges and the variation degree of TDS level on feedback level changing.The results show that the CSHR microcavity laser can respond to the feedback level of 0.07%,corresponding to-63-dB feedback strength.Compared to conventional distributed feedback laser,the sensitivity improves almost 20 dB due to the shorter internal cavity length of CSHR microcavity laser.Moreover,1%feedback level changing will induce 1.001 variation on TDS level,and this variation degree can be influenced by other critical internal parameters(active region side length,damping rate,and linewidth enhancement factor).

Periodic and chaotic oscillations in mutual-coupled mid-infrared quantum cascade lasers

Dynamic states in mutual-coupled mid-infrared quantum cascade lasers(QCLs) were numerically investigated in the parameter space of injection strength and detuning frequency based on the Lang-Kobayashi equations model. Three types of period-one states were found, with different periods of injection time delay τ_(inj), 2τ_(inj), and reciprocal of the detuning frequency. Besides, square-wave, quasi-period, pulse-burst and chaotic oscillations were also observed. It is concluded that external-cavity periodic dynamics and optical modes beating are the mainly periodic dynamics. The interaction of the two periodic dynamics and the high-frequency dynamics stimulated by strong injection induces the dynamic states evolution.This work helps to understand the dynamic behaviors in QCLs and shows a new way to mid-infrared wide-band chaotic laser.