锂-硫二次电池界面反应的特殊性与对策分析

锂-硫电池是在现有锂离子电池基础上最可能实现储能密度大幅提升的实用二次电池体系. 然而,这一电池体系的电化学利用率与循环稳定性仍然难以满足应用要求. 造成锂-硫电池性能不稳定的原因在于硫正极和锂负极的材料结构和反应环境始终处于变化之中,如在充放电过程中,硫-碳反应界面的电化学阻塞、中间产物的溶解流失、正负极之间的穿梭效应等副反应导致正极与负极均难形成稳定的电化学反应界面。针对这些特殊问题,本文简要分析了影响能量利用率和循环稳定性的化学与电化学机制,并提出了构建稳定锂负极与高效硫正极的若干可行性技术.     

LiAl_yNi_(1-y)O_2作为锂离子电池正极材料的研究

本文采用固相反应法合成了一系列不同 y值的LiAlyNi1- yO2 材料 ,通过对其电化学性能的研究发现 ,在适当的烧结条件下 ,LixAl0 .2 5 Ni0 .75 O2 作为二次锂离子电池的正极材料 ,其耐过充性和循环性能都有明显改善 .当Li含量大于 1时 ,在高电位范围充放 (3- 4 .8V) 30次循环后仍保持着首次放电容量的 95 % ,而LiNiO2 在此电压范围内经 2 0次循环后却只有首次放电容量的 5 6 % .通过循环伏安实验表明 :性能改善的主要原因可能是由于充电过程中 ,Al3+ 的掺杂阻止了LixAl0 .2 5Ni0 .75 O2 随Li+ 离子过量脱出而发生晶型转变 .     

Ag掺杂LiFePO_4/C正极材料的结构及电化学性能

用真空固相反应与液相还原结合的方法,合成了锂离子电池正极材料——金属银掺杂的覆碳磷酸铁锂(LiFePO4/Ag/C),用X射线衍射、扫描电镜、循环伏安、交流阻抗等技术研究其结构、形貌及电化学性能。结果表明,该正极材料为橄榄石型晶体、类球形颗粒(粒径范围约为0.5~2.0μm);Ag掺杂能使合成的LiFePO4颗粒粒径更小、分布更均匀,有效地提高其电化学循环性能;LiFePO4/Ag/C电极0.1C倍率充放的首次放电比容量为138.2mAh/g,50次循环的放电比容量为130.1mAh/g,最高放电比容量为148.3mAh/g;LiFePO4/Ag/C正极材料具有良好的锂离子传导性能,其锂离子扩散系数(DLi+)为8.94×10-15cm2/s。     

聚阴离子掺杂LiMnO_(2-y)X_y(X=BF_4~-,SiO_3~(2-),MoO_4~(2-),PO_4~(3-),BO_3~(3-))材料的合成及其电化学性能

采用水热法合成了聚阴离子掺杂LiMnO2-yXy(X=BF4-,SiO32-,MoO42-,PO43-,BO33-,y=0.01、0.03、0.05)锂离子电池正极材料。通过X射线粉末衍射(XRD)、X光电子能谱(XPS)、扫描电镜(SEM)和恒电流充放实验,研究了不同掺杂离子和掺杂量对产物结构和电化学性能的影响。结果表明,少量聚阴离子的掺杂未改变正交LiMnO2的晶体类型,但增大了材料晶胞体积,改善了材料的电化学循环性能。电化学交流阻抗(EIS)测试结果表明,聚阴离子掺杂增大了材料电荷转移阻抗,但明显提高了材料中Li+的扩散能力。     

溶胶凝胶法合成LiCuVO4及其电化学性能研究

以CH3COOLi.2H2O、Cu(NO3)2.3H2O、V2O5和双氧水(30%)为原料,采用溶胶凝胶法合成了LiCuVO4,其结构、组成和形貌经XRD和SEM确认。结果表明,本文所合成的LiCuVO4具有隧道结构的形貌,颗粒粒径为0.2～6μm。将LiCuVO4作为锂离子电池正极材料,首次循环的放电比容量达到160mAh/g;而作为负极材料,其最大放电比容量达到481mAh/g。在两种电化学测试中,LiCuVO4都显示了良好的循环性能。     

表面覆CoOOH的球形Ni(OH)_2的制备及快充性能

应用化学沉淀-电化学氧化法,于球形N i(OH)2颗粒表面生成CoOOH包覆层,研究包覆处理对AA型高容MH/N i电池快充性能的影响,并由红外光谱和扫描电镜表征覆钴样品.结果表明,以包覆CoOOH的N i(OH)2作正极活性材料装配的电池较之于正极单一添加CoO的电池,其内阻降低了约3.4 mΩ,该电池快充时充电电压平台较低且在充电末期电池温度不超过55℃,首次放电效率达90.6%,快充循环寿命达300周次.     

三氧化钼——一种新型有机系钠离子储能器件负极材料

由于锂资源短缺,我们尝试使用三氧化钼作为钠离子储能装置负极材料。通过一种简单的方法合成了三氧化钼,使用XRD、SEM和TEM等测试手段对其物性进行了表征。利用三氧化钼作为有机系钠离子储能器件的负极材料,通过循环伏安和恒流充放电测试探讨了负极材料的储钠机理。以三氧化钼(MoO3)作为负极材料,活性炭(AC)和石墨(graphite)作为正极材料,组装成新型的电化学储能器件,研究了两种器件在1mol/L NaPF6的碳酸丙烯酯(PC)中的电化学性能。两种器件的电压范围分别为0~3.2V和0~3.5V,能量密度最高可分别达到31.6和53 Wh/kg,长循环性能远远优于AC/AC对称电容器。此种储能装置有望成为锂离子电池的一个很好的替代。     

镍氢电池的循环性能与活性物质微结构的研究

与循环试验大致同步, 用静态(初态和终态)或准动态(增加若干个中间态)的模式对MH/H电池循环性能、电极(包括负极和正极)材料的微结构进行了X射线衍射(XRD)研究, 发现循环性能衰减与正极材料β-Ni(OH)₂的点阵参数、平均晶粒尺度、微应变和总的层错几率均随循环周期增加而减小以及负极材料中腐蚀产物A(OH)₃和B相出现和增加有一定的对应关系, 发现MH/Ni 电池循环性能的衰减是正极材料和负极材料的结构和微结构随着循环次数的增加发生明显变化, 恶化了正负极材料的电化学性能, 同时消耗和恶化了电解液的综合结果. 为了提高电池的循环性能, 采用不同正极材料的添加剂. 结果表明, CaF₂和Lu₂O₃有明显的效果, 其中CaF₂效果最好, 并有广泛的实用性.     

可充镁电池正极材料PTMA/石墨烯

本文制备了聚4-甲基丙烯酸-2,2,6,6-四甲基哌啶-1-氮氧自由基酯(PTMA)/石墨烯纳米复合材料,并报道了其作为可充镁电池正极材料的电化学性能.通过傅里叶变换红外(FTIR)光谱、扫描电镜(SEM)、透射电镜(TEM)表征复合材料的结构和形貌;循环伏安和恒电流充放电测试其电化学性能.粒径10 nm左右的PTMA颗粒分散在具有导电作用的石墨烯表面;在"一代"电解液Mg(AlCl2BuEt)2/四氢呋喃(THF)(0.25 mol L-1)中,22.8mA g-1充放电电流密度下,PTMA/石墨烯复合材料的起始放电容量可达到81.2 mAh g-1.研究结果表明,含有自由基的有机化合物可以作为可充镁电池的一类新型正极材料,可以进一步通过使用具有高氧化分解电压的电解液来提高其放电容量.     

Li_4Ti_5O_(12)纳米片的合成及储锂性能研究

以无定形的水合二氧化钛为前驱物,水热法合成了200～400nm大小的Li4Ti5O12纳米片作为锂离子电池负极材料.XRD(X射线衍射)、SEM(扫描电子显微镜)和TEM(透射电镜)分析表征样品的物相结构、表观形貌;循环伏安、充放电循环和电化学交流阻抗技术分别测定该纳米Li4Ti5O12在有机电解液和室温离子液体S114TFSI电解液中的电化学性能.结果表明,该材料具有较高的放电容量和良好的循环性能,有望成为锂二次电池新型负极材料.     

尼龙6/抗菌蛭石复合材料的制备及性能研究

通过离子交换法对蛭石进行载银和有机化改性,制备出3种抗菌蛭石,进一步采用熔融共混法制备了尼龙6/抗菌蛭石复合材料,测试了复合材料的抗菌性能和物理力学性能,利用TEM和SEM观察了蛭石在尼龙6中的分散情况和拉伸断面.研究结果表明,载银并有机化的蛭石与尼龙6的复合材料对大肠杆菌和金黄色葡萄球菌均具有明显的抑菌圈,对大肠杆菌...     

A composite polyaniline/graphene–coated polyamide6 nanofiber mat for electrochemical applications

In this study, polyamide6 (PA6) nanofiber mats were fabricated through the electrospinning process. The nanofibers were coated by polyaniline (PANI) using the in situ polymerization of aniline in the presence of graphene oxide. The composite of the PANI/graphene oxide–coated nanofiber mat was treated with hydrazine monohydrate to reduce graphene oxide to graphene, and this was followed by the reoxidation of PANI. Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), wide angle X‐ray diffraction (WAXD), thermal gravimetric analysis (TGA), tensile strength tests, electrical conductivity measurements, cyclic voltammetry (CV), and charge/discharge measurements were conducted on the composite PA6/graphene nanofiber mats. It was found that the surface of the PA6 nanofibers was coated uniformly with the granular PANI and graphene oxide. Besides, the composite nanofibers showed good tensile and thermal properties. Their electrical conductivity and specific capacitance, when used as a separator in the cell, were 1.02 × 10^?4 S/cm and 423.28 F/g, respectively. Therefore, the composite PANI/reduced graphene oxide–coated PA6 nanofiber mats could be regarded as suitable candidates for application in energy storage devices.     

The mechanical properties of plasma‐treated carbon fiber reinforced PA6 composites with CNT

The aim of this work is the evaluation of the effects of plasma treatment and the addition of CNT on the mechanical properties of carbon fibre/PA6 composite. A powder impregnation process with integrated inline continuous plasma of carbon fibers was used to produce CF/PA6 composite. CF/PA6 composite was processed into test laminates by compression moulding, and interface dominated composite properties were studied. The tensile and impact strength of composites containing CNT and plasma‐treated carbon fibres improved obviously. The tensile strength of nanocomposite largely increases with the increasing of the CNT content and then decreases when the CNT content is over 2%. The hydroxyl groups of the fibers surface are in favor of the wettability of carbon fibers by the polar matrix resin, which is resulting in a further interaction of the fiber surface with the curing system of the matrix resin.     

碳纤维复合聚乙炔膜合成及其p-型电池的性能

聚乙炔(PA)膜作为电极材料实用化的主要困难在于稳定性较差.虽然对这一问题进行了不少研究,但至今成效不大.我们从提高聚乙炔膜的强度、导电性及整体电流分布出发,用冷等离子体方法首次合成了碳纤维复合聚乙炔膜.结构分析结果表明,在复合膜中碳纤维和聚乙炔形成了一定程度的接枝,其空气和热稳定性均高于纯PA膜.用这种膜构成的p-型电池具有较高的化学掺杂度,各项电性能均有所提高.     

Complementary effects of multiwalled carbon nanotubes and conductive carbon black on polyamide 6

This article introduces a newly innovative idea for preparation of superconductive ternary polymeric composites of polyamide 6 (PA6), conductive carbon black (CCB), and multiwalled carbon nanotubes (MWCNTs) with different weight ratios by a melt‐mixing technique. The complementary effects of CCB and MWCNTs at different compositions on rheological, physical, morphological, thermal, and dynamic mechanical and electrical properties of the ternary composites have been examined systematically. We have used a novel formulation to produce high‐weight fraction ternary polymer composites that show extremely higher conductivity when compared with their corresponding binary polymer composites at the same carbon loading. For example, with an addition of 10 wt % MWCNTs into the CCB/PA6 composite preloaded with 10 wt % CCB, the electrical conductivity of these ternary composites was about 5 S/m, which was 10 times that of the CCB/PA6 binary composite (0.5 S/m) and 125 times that of the MWCNT/PA6 binary composite (0.04 S/m) at 20 wt % carbon loading. The incorporation of the MWCNTs effectively enhanced the thermal stability and crystallization of the PA6 matrix in the CCB/PA6 composites through heterogeneous nucleation. The MWCNTs appeared to significantly affect the mechanical and rheological properties of the PA6 in the CCB/PA6 composites, a way notably dependent on the MWCNT contents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1203–1212, 2010     

Tissue engineering scaffold material of nano-apatite crystals and polyamide composite

A new kind of tissue engineering scaffold materials of needle-like nano-hydroxyapatite (n-HA) and polyamide (PA) biocomposite is prepared by co-solution, co-precipitation method and water treatment under normal atmospheric pressure. The n-HA crystals uniformly distribute in the composite with a crystal size of 10-20 nm in diameter by 70-90 nm in length. The n-HA/PA composite has good homogeneity, high n-HA content (65 wt%), and high bioactivity. Strong molecule interactions and chemical bondings are present between the n-HA and PA in the composite, which are verified by IR, XPS and XRD. The composite has excellent mechanical properties close to the natural bone. The porous 3-D scaffold is made by injection foaming method, which has not only macropores, but also micropores on the walls of macropores. The porosity is 80% and the average macropore diameter is about 300 μm of the composite.The n-HA/PA composite can be used for tissue engineering and bone repair or substitute.     

Evaluation of mechanical properties and characterization of silicon carbide–reinforced polyamide 6 polymer composites and their engineering applications

In this article, the tensile strength, impact, and hardness properties of silicon carbide (SiC) reinforced with polyamide 6 (PA6) are described for the first time. The composites were fabricated by an injection molding method using the SiC with varying weight percentages. The tensile and hardness of SiC/PA6 composites showed a regular trend of increasing tensile strength, impact, and hardness properties with varying weight percentages until 10 wt% and impact strength of SiC/PA6 composites increased up to 5 wt% afterwards decreasing the mechanical properties of the composite with greater weight percentages. Scanning electron microscope (SEM) studies were carried out to evaluate the SiC/PA6 interactions. The results related to SiC/PA6 composites were compared with those obtained for pure PA6.     

聚丙烯/尼龙6挤出原位成纤后的牵引作用

用挤出机共混挤出聚丙烯和尼龙6，加工中尼龙6作为分散相在聚丙烯中形成微纤。改变挤出物挤出模口后所受的牵引作用的速度会产生材料形态与力学性能的变化。发现随牵引速度的提高，尼龙6微纤的平均直径变小，尺寸分布更均匀，力学性能也随之提高。差热分析表明，随牵引速度的增加聚丙烯与尼龙6的相容性略有提高，X-射线衍射分析表明拉伸作用对尼龙纤维晶体中分子链的取向无影响。     

Effect of maleic anhydride‐grafted polytetrafluoroethylene on the tensile and tribological properties of blending polytetrafluoroethylene with polyamide‐6

Blending polytetrafluoroethylene (PTFE) to polyamide‐6 (PA6) with and without maleic anhydride‐grafted polytetrafluoroethylene (PTFE‐g‐MA) was produced in a corotating twin screw extruder, where PTFE acts as the polymer matrix and PA6 as the dispersed phase. The effect of PTFE‐g‐MA on the tensile properties and tribological propertiesof PTFE/PA6 polymer blends is studied. Results show that the structural stability and morphology of the blends were greatly improved by PTFE‐g‐PA6 grafted copolymers, which were formed by the in situ reaction of anhydride groups with the amino end groups of PA6 during reactive extrusion forming an imidic linkage. The presence of PTFE‐g‐PA6 in the PTFE continuous phase improves the interfacial adhesion, as a result of the creation of an interphase that was formed by the interaction between the formed PTFE‐g‐PA6 copolymer in situ and both phases. Compared with thePTFE/PA6 without PTFE‐g‐MA, the PTFE/PA6 with PTFE‐g‐MAhad the lowest friction coefficient and wear under given applied load and reciprocating sliding frequency. The interfacial compatibility of the composite prevented the rubbing‐off of PA6, accordingly improved the friction and wear properties of the composite. Copyright © 2009 John Wiley & Sons, Ltd.     

The addition of clay on the mechanical properties of surface‐treated CF‐filled PA66 composites

Polyamide 66 (PA66) composites filled with clay and carbon fiber (CF) were prepared by twin‐screw extruder in order to study the influence of nanoparticle reinforcing effect on the mechanical behavior of the PA66 composites (CF/PA66). The mechanical property tests of the composites with and without clay were performed, and the fracture surface morphology was analyzed. The results show that the fracture surface area of the clay‐filled CF/PA66 composite was far smoother than that of the CF/PA66 composite, and there formed a tense interface on the CF surface after the addition of clay. The tensile and flexural strength of CF/PA66 composites with clay was improved. The impact strength decreased because of the high interfacial adhesion. In conclusion, the addition of clay favored the improvement of the higher interface strength and so had good effect on improving the tensile and flexural properties of the composites. Copyright © 2017 John Wiley & Sons, Ltd.