吡咯量对原位聚合控制结晶法制备LiFePO4/C正极材料的影响

以原位聚合聚吡咯控制结晶法合成的介孔FePO4/PPy为前躯体制备了锂离子电池纳米LiFePO4/C正极材料.用X射线衍射、扫描电子显微镜、透射电子显微镜以及充放电测试和交流阻抗等研究了吡咯用量对合成材料的结构、形貌和电化学性能的影响.结果表明:LiFePO4/C正极材料与FePO4/PPy前驱体有相似的形貌,吡咯的用量对材料的电化学性能影响较大,当吡咯的加入量为1.0mL时,材料粒径较小,分布均匀,电化学性能最优,在0.1C倍率下的放电比容量为149.0 mA·h/g,且循环过程中容量保持率高.     

基于β-FeOOH纳米棒制备LiFePO_4/C和Fe_2O_3纳米电极材料及其电池性能

自制直径为90nm、长为500nm的β-FeOOH纳米棒为前驱物,通过碳热还原法和热分解法分别制备出形貌均匀、粒径为300nm的LiFePO4/C正极材料和粒径为100nm的Fe2O3负极材料,并研究它们对金属锂组成半电池和构造LiFePO4/C vs.Fe2O3全电池的电化学性能。结果表明：LiFePO4/C半电池在0.1C、0.5C、1.0C、5.0C、10.0C和15.0C（1C=170 mA g–1）倍率下放电比容量分别为158.8、153.2、144.3、126.8、111.0 mA h g–1和92.9mA h g–1。经过不同倍率循环后,返回0.1 C放电比容量为157.5mA h g–1,为初始0.1 C放电比容量的99.2%。Fe2O3半电池在50mA g–1电流密度下首次放电比容量为1655.5mA h g–1,循环50次后,仍保持460mA h g–1的放电比容量。LiFePO4/C vs.Fe2O3全电池在0.1 C倍率下,相对于LiFePO4活性物质,首次放电比容量为148.7mA h g–1;相对于Fe2O3活性物质,首次放电比容量为441.7mA h g–1。由LiFePO4/C纳米粒子作为正极材料、Fe2O3纳米粒子作为负极材料组成的全电池在0.1 C到2.0 C不同倍率下均表现出了良好的循环性能,且返回0.1 C后其放电比容量相对于初始0.1 C放电比容量无衰减。可见,以β-FeOOH纳米棒为前驱物控制制备的LiFePO4/C正极纳米材料和Fe2O3负极纳米材料可以有效地提升电池的性能。     

Li_2FeSiO_4/C复合材料的制备及电化学性能

以CH3COOLi、FeC2O4、纳米SiO2为原料,葡萄糖为碳源,超导碳为微波耦合剂,采用微波加热法合成了Li2FeSiO4/C材料。考察了不同微波时间对材料室温下电化学性能的影响,并通过X射线衍射、扫描电子显微镜、透射电子显微镜和X射线能谱对样品的晶型结构、表面形貌和组成进行表征分析。结果表明,微波合成法可以快速制备Li2FeSiO4/C材料,微波时间16min所得样品具有最好的电化学性能。室温下以C/16倍率进行充放电测试,放电容量为111.5mA·h/g;以0.2C进行充放电循环,首次放电容量为96.7mA·h/g,19次循环后容量仍有95.2mA·h/g。     

改进固相法合成LiNixCoyMn1-x-yO2正极材料及性能研究

采用同相法制备正极材料LiNi1/3Co1/3Mn1/3O2,用X射线衍射仪(XRD)、扫描电子显微镜(SEM)/透射电镜(TEM)分析材料的结构和形貌特征,用LAND电池测试系统测试材料的电化学性能(充放电容量和循环性能等).以LiOH·H2O,H2C2O4·2H2O,Ni(AC)2·4H2O,Co(AC)2·4H2O和Mn(AC)2·4H2O为原料,采用固相法在不同煅烧温度和煅烧时间下制备的层状正极材料LiNi1/3Co1/3Mn1/3O2具有典型的α-NaFeO2型层状结构特征,晶型结构完整.电化学性能测试结果表明,在850℃下保温15 h合成的正极材料电化学性能最优,在电流密度为120 mA/g、充放电电压在2.75～4.5 V时,经30次循环后放电比容量为163.5 mA·h/g,容量保持率为94%;50次循环后为157.2 mA·h/g,容量保持率为90.8%.     

离子热法制备Li4Ti5O12负极材料及其电化学性能

以醇胺类离子液体二乙醇胺乙酸盐为反应介质,钛酸四丁酯与乙酸锂为原料,低温常压下合成前驱体,再在高温下制备Li4Ti5O12负极材料.用X射线衍射、扫描电子显微镜和恒电流充放电分别测定材料的结构、形貌以及材料的电化学性能.结果表明:在700℃烧结12h,所得样品具有300nm的粒径,并表现出优良的电化学性能,在0.1C倍率下放电容量为162.8 mA·h/g,20次循环后比电容量保持在150.3 mA.h/g.     

正极材料LiFe1-xNixPO4/C的合成及性能

以H3PO4、FeSO4·7H2O和LiOH·H2O为原料,采用水热法以Ni(CH3COO)2·4H2O为镍源、葡萄糖为碳源,合成锂离子电池正极材料LiFe1-xNixPO4/C(x=0,0.02,0.05,0.08).采用X射线衍射、扫描电子显微镜对材料晶体结构和表观形貌进行表征,利用充放电测试技术对其电化学性能进行测定.结果表明:掺杂适量的Ni2+可以减小材料的晶胞体积,提高材料的比电容和循环性能.当Ni2+的掺杂量为5.0％时,LiFe0.95Ni0.05PO4/C材料在0.1C倍率下的首次放电比电容可达到152.8 mA·h/g,经过20次循环后的比电容保持率在97.5％以上.     

前驱体FePO_4的制备工艺及其对流变相法合成LiFePO_4/C正极材料的影响

以FeSO4·7H2O,NH4H2PO4,H2O2和NH3·H2O为原料,采用均相沉淀法制备前驱体FePO4·2H2O,再通过流变相法制得LiFePO4/C复合材料,研究了反应温度、搅拌速度和pH值等反应条件对合成LiFePO4/C的影响。采用XRD、SEM和恒流充放电方法表征了材料的结构、形貌和电化学性能。结果表明:当反应温度为60℃,搅拌速度为800 r/min,pH值为2.5时,合成的LiFePO4/C为纯相,且粒度均匀,粒径约为200 nm,在0.1 C充放电倍率下,其首次放电比容量达137 mAh/g。     

前驱体FePO4的制备工艺及其对流变相法合成LiFePO4/C正极材料的影响

以FeSO4·7H2O,NH4H2PO4,H2O2和NH3·H2O为原料,采用均相沉淀法制备前驱体FePO4·2H2O,再通过流变相法制得LiFePO4/C复合材料,研究了反应温度、搅拌速度和pH值等反应条件对合成LiFePO4/C的影响。采用XRD、SEM和恒流充放电方法表征了材料的结构、形貌和电化学性能。结果表明:当反应温度为60℃,搅拌速度为800 r/min,pH值为2.5时,合成的LiFePO4/C为纯相,且粒度均匀,粒径约为200 nm,在0.1 C充放电倍率下,其首次放电比容量达137 mAh/g。     

离子热法制备镍掺杂LiFePO4正极材料及其性能

以二乙醇胺乳酸盐为反应介质,采用离子热法在180℃制备LiFePO4和LiFe0.95Ni0.05PO4,利用蔗糖在650℃分解覆炭得到LiFe0.95Ni0.05PO4/C复合材料。结果表明:LiFePO4及其掺杂改性物均为橄榄石晶体结构,少量Ni的掺杂导致材料粒度和形貌变化,短轴尺寸约为300nm的棒状材料变为尺寸约为200nm的纺锤体状复合材料。恒电流充放电测试结果表明:在室温及0.1C倍率下,LiFePO4、LiFe0.95Ni0.05PO4和LiFe0.95Ni0.05PO4/C首次放电比容量分别为135.2、140.1mA h/g和165.4 mA h/g,LiFe0.95Ni0.05PO4/C在不同倍率下循环30次均无明显衰减。     

锂离子电池正极材料LiFePO4的制备及电化学性能研究

以Li3PO4和Fe（3PO4）.28H2O为原料,采用固相法成功制备了锂离子电池正极材料LiFePO4,并讨论了Li3PO4用量对材料的影响。采用X射线衍射（XRD）、扫描电子显微镜（SEM）和充放电测试等手段对最终产物的物相、形貌和电化学性能进行了表征。结果表明,按计量比制备的LiFePO4样品具有较好的电化学性能,以0.1、0.5、1和5 C（1C=150 mA/g）的倍率进行充放电,首次放电比容量分别为135.6、123.8、116.2和56.5 mAh/g。磷酸锂过量8%制备的样品具有较好的高倍率性能,5C时放电比容量为80.3 mAh/g;而磷酸锂过量30%的样品则具有很好的小倍率放电比容量,0.1C时放电比容量为151.1 mAh/g。     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

ICP-MS法测定地球化学样品中As、Cr、Ge、V等18种微量痕量元素的研究

建立了测定地球化学样品中包括As、Cr、Ge、V等18种微量、痕量元素的ICP-MS方法。地化试样用HF-HNO3混酸分解后,以1 1 HNO3溶解干渣。由于制样不使用盐酸,避免了Cl对As、Cr、Ge、V的质谱干扰。用国家一级地球化学标准物质GBW 07309制备溶液优化仪器工作参数,并用于校准。方法测定限(6s)为:0.007~6.4μg/g,精密度(RSD%,n=12)为:29%~9.4%,经过国家一级地球化学标准物质的分析验证,结果与标准值吻合。方法已应用于国土资源调查的试样分析。