不同碳源掺杂磷酸亚铁锂正极材料电化学性能研究

采用液相共沉淀-固相焙烧合成了橄榄石型磷酸亚铁锂(LiFePO4)正极材料,用X射线衍射(XRD)、扫描电镜(SEM)和恒流充放电测试等方法对产物物相结构、表观形貌和电化学性能进行了表征和分析.纯相材料首次放电比容量达到90.6 mA·h/g,循环5次后,放电比容量为75.94 mA·h/g.为解决首次放电比容量低下以及材料循环性能差的问题,采取不同碳源掺杂对材料进行改进,最后得到LiFePO4/C复合正极材料,0.05 C首次放电比容量达到158.8 mA·h/g.     

玉米棒状LiFePO4正极材料的离子热法制备及性能

以自制离子液体为反应介质,FeSO4·7H2O、(NH4)2HPO4和LiOH·H2O为原料,采用离子热法制备了LiFePO4,并经过热处理覆炭制备出LiFePO4/C复合材料。利用X射线衍射、扫描电子显微镜、透射电子显微镜表征了材料的结构和形貌,采用恒电流充放电测试其充放电性能。结果表明:常压低温下所制备的LiFePO4正极材料和经热处理制备的LiFePO4/C都具有橄榄石晶体结构,呈玉米棒状形貌,并表现出优良的充放电性能。室温下,0.1C倍率下LiFePO4和LiFePO4/C首次放电比容量分别为140.7 mA·h/g和162.5 mA·h/g。LiFePO4/C在0.1、1 C和5 C倍率下循环30次均无明显衰减。     

液相法合成高容量LiFePO4/C复合正极材料

采用液相共沉淀法合成了纯相橄榄石型LiFePO4和LiFePO4/C复合正极材料。利用原子吸收(AAS)、X射线衍射(XRD)、扫描电镜(SEM)、振实密度测定等方法对其进行表征,并组装成电池研究其电化学性能。结果表明:LiFePO4和LiFePO4/C都具有单一的橄榄石型晶体结构,且前者的振实密度可达1.67 g/cm2,掺碳后制成的LiFePO4/C振实密度有所降低,但充放电平台非常平稳。与纯相LiFePO4相比,LiFePO4/C具有更高的放电比容量和循环性能,室温下以0.2 mA/cm2和0.4 mA/cm2电流密度充放电,首次放电比容量分别达到158.1 mA.h/g、150.0 mA.h/g。充放电循环20次后放电比容量仍分别保持在154.2 mA.h/g,137.2 mA.h/g。     

LiNO3-TiO2-尿素体系燃烧合成锂离子电池负极材料Li4Ti5O12及电化学性能

以纳米TiO2和LiNO3为原料,尿素为燃料,燃烧法合成了锂离子电池负极材料Li4Ti5O12. 利用XRD、SEM和恒电流充放电、循环伏安和交流阻抗对其进行表征. 结果表明,预设炉温850℃,尿素与锂摩尔比1,焙烧8 h,制备得到平均粒径小于500 nm、粒度分布均匀的纯相尖晶石型结构Li4Ti5O12,并具有良好的电化学性能,具有1.5 V充放电平台,在0.1 C倍率下(1 C=170 mA·h/g),其首次充放电容量达到168 mA·h/g,经过100次循环后放电比容量仍有162 mA·h/g,容量保持率96.4%.     

低温熔盐燃烧法合成LiNi_(0.5-x)Mg_xMn_(1.5)O_4(x=0,0.05)及其电性能

为了快速、高效地制备5V锂离子电池正极材料,采用低温熔盐燃烧法合成了LiNi0.5Mn1.5O4粉末。X射线衍射分析表明:使用该方法,将原料在600℃焙烧1h即可获得单相LiNi0.5Mn1.5O4材料,Mg的掺杂有利于产物结晶性的提高。扫描电子显微镜观察表明,LiNi0.45Mg0.05Mn1.5O4的粒径为亚微米级的,且粒径分布均匀。制成电极后电性能研究表明,在3.5～5.0V的电压范围,75mA/g的电流密度下,该材料进行50次充放电循环后,放电比容量没有明显衰减。微量的Mg掺杂,可以提高样品的放电比容量,改善材料的首次充放电效率并提高材料的放电平台。600℃下焙烧5h所制备的LiNi0.45Mg0.05Mn1.5O4首次放电比容量为134(mA·h)/g,在电流密度为75mA/g下进行50次循环后保持率达100%。     

共沉淀法合成磷酸铁锂掺碳复合正极材料

采用共沉淀法合成了纯相橄榄石型磷酸铁锂(LiFePO4)和磷酸铁锂掺碳(LiFePO4/C)复合正极材料.利用X射线衍射(XRD)、原子吸收(AAS)、扫描电镜(SEM)、红外吸收(FT-IR)、振实密度测定等方法对其进行表征,并组装成电池研究其电化学性能.结果表明:HFePO4和LiFePO4/C具有单一的橄榄石型晶体结构,前者的振实密度可达1.58 g/cm2,LiFePO4/C振实密度有所降低,但充放电平台非常平稳.与纯相LiFePO4相比,LiFePO4/C具有更高的放电比容量和循环性能,室温下以0.05 C和0.1 C倍率电流充放电,首次放电比容量达到158.1,150.0 mA·k/g.充放电循环20次后放电比容量仍保持在154.2,137.2 mA·h/g.     

水热法制备Al/Co共掺杂VO2(B)正极材料及其电化学性能

采用水热法,以V_2O_5、C_(12)H_(22)O_(11)、Co(NO_3)_2·6H_2O、Al(NO_3)_3·9H_2O为原料,分别合成了纯相VO_2(B)和Al/Co共掺杂VO_2(B)。X射线衍射分析结果显示,掺杂后样品的衍射峰强度变低、峰形变宽、结晶性下降。扫描电子显微镜照片显示,掺杂后样品的形貌发生明显变化,由长棒状(纯相)变为短棒状与片状均匀混合的形貌。电化学性能测试结果显示首次放电比容量和循环性能都大幅度提高。样品A1(摩尔比n(Al):n(Co):n(V)=12:6:100)首次放电比容量为301 mA·h/g,比未掺杂样品(216 mA·h/g)高85 mA·h/g;样品A2(摩尔比n(Al):n(Co):n(V)=12:12:100)首次放电比容量为285 mA·h/g,比未掺杂样品高69 mA·h/g,并且掺杂样品经过100次充放电循环后容量保持率都比未掺杂样品高。     

锂离子电池正极材料Li3V2[(PO4)1-xFx]3/C的合成及性能表征

以LiH2PO4、LiF和V2O5为原料,蔗糖为还原剂,用碳热还原法合成了Li3V2[(PO4)1-xFx]3/C(x=0、0.02、0.05、0.08、0.10和0.15),并用X射线衍射、Fourier变换红外光谱、循环伏安、交流阻抗谱和恒流充放电技术研究了F-掺杂对材料结构和电化学性能的影响.结果表明:F-掺杂Li3V2(PO4)3/C与纯Li3V2(PO4)3/C均为单斜结构,但少量的F-掺杂可提高电极反应可逆程度和电导率,降低电荷传递阻抗;在所得的F-掺杂材料中,Li3V2[(PO4)0.95F0.05]3/C具有较好的电化学性能.在3.0～4.2V (vs.Li/Li+)循环时,电极的0.5C放电容量为124.4 mA·h/g,50次循环后容量保持率为98.5％,15C下的放电容量为84.7mA·h/g,50次循环后容量保持率为97.4％,而Li3V2(PO4)3/C的仅为59.2 mA·h/g和89.0％.     

微波辅助溶胶-凝胶法合成锂离子电池负极材料Li_4Ti_5O_(12)

以微波辅助溶胶-凝胶法合成Li4Ti5O12、Al或C掺杂的Li4Ti5O12样品。用X射线衍射仪、扫描电子显微镜分别表征所得产物的结构和形貌,研究不同样品在恒流充放电条件下的电化学性能。结果表明:合成Li4Ti5O12粉体的最佳微波处理条件为800℃、40min;微波热处理合成样品颗粒尺寸为100nm左右,掺Al或C样品颗粒的分散性要优于未掺样品的。首次充放电结果表明:所有样品的放电平台平稳,掺Al或C样品的首次放电容量均高于未掺样品的,掺C样品的首次放电容量为162mA·h/g,更接近Li4Ti5O12的理论容量(175mA·h/g)。     

掺杂与表面包覆对尖晶石型LiMn2O4电化学性能的影响

用固相法制备了Cr3 和F-同时掺杂的尖晶石型LiMn2O4正极材料,并对掺杂材料进行氧化铝表面包覆改性,用扫描电子显微镜和X射线衍射研究了材料的表面形貌和晶体结构,用充放电实验和交流阻抗技术测试了材料的电化学性能。结果表明:LiMn2O4在掺杂Cr3 和F-及表面包覆氧化铝后仍为尖晶石型结构,随掺杂和包覆量的增加,材料首次放电容量降低,但循环性能明显改善,其中未掺杂、掺杂量为0.10和表面包覆0.3%的氧化铝的材料室温首次放电容量分别为125.3 mA·h/g、117.5 mA·h/g和113.7 mA·h/g,循环25次后容量保持率分别为82.7%、91.5%和93.6%,而55℃下25次循环后放电容量及其保持率以表面包覆氧化铝的最佳,分别达到104.2 mA·h/g和92.1%。     

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.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料,介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比,介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序,对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。