Structural, electrochemical and thermal properties of LiNi0.8−yTiyCo0.2O2 as cathode materials for lithium ion battery

Multiple substitution compounds with the formula LiNi_0.8−yTi_yCo_0.2O₂ (0≤y≤0.1) were synthesized by sol-gel method using citric acid as a chelating agent. The effects of titanium substitution on the structural, electrochemical and thermal properties of the cathode materials are investigated. A solid solution phase (R-3m) is observed in the range of 0≤y≤0.1 for the titanium-doped materials. X-ray photoelectron spectroscopy (XPS) shows that there are Ni³⁺, Ni²⁺, Co³⁺, Co²⁺ and Ti⁴⁺ five transition metal ions in titanium-doped materials. Rietveld refinement of X-ray diffraction (XRD) patterns indicates that titanium substitution changes the materials’ structure with different cationic distribution. An increase of the Ni/Co amount in the 3a Li site is found with the addition of titanium amount. An improved cycling performance is observed for titanium-doped cathode materials, which is interpreted to a significant suppression of phase transitions and lattice changes during cycling. The thermal stability of titanium-doped materials is also improved, which can be attributed to its lower oxidation ability and enhanced structural stability at delithiated state.     

Assessment of the relative agronomic effectiveness of phosphate rocks under glasshouse conditions

Six phosphate rocks (PRs) of varying reactivities were compared with monocalcium phosphate (MCP) in a glasshouse experiment growing perennial ryegrass (Lolium perenne cv. Nui) as the test plant on four soils of contrasting P sorption capacity and exchangeable Ca. The cumulative dry matter yield over 10 harvests showed a significant response to P application in all soils. Based on relative yield and P uptake, MCP was the most effective P fertilizer followed by the reactive phosphate rocks, which were superior to the unreactive rocks in all soils. The relative agronomic effectiveness (RAE) and substitution ratio (SR) of individual PR fertilizers, calculated with respect to MCP using the methods of vertical and horizontal comparison, respectively, were similar over a range of fertilizer rate. There was a decline or slight increase in the performance of PRs with time in the low P sorption soils but a consistent increase in the high P sorption soils. Some initial influence of exchangeable Ca content of the soils on the relative performance of PRs was also observed. Generally the PRs performed better in high P sorption soils than low P sorption soils and in low exchangeable Ca soils than high exchangeable Ca soils.     

Hyperbranched Polymers Containing Cyclopentadienyliron Complexes

A number of hyperbranched polymers containing cyclopentadienyliron moieties were prepared using the A₂+B₃ method. The A₂ compounds used were common diols, dithiols or dichloroarenecomplexes. B₃ compounds included either prepared star-shaped molecules or a purchased triol. The effect of the reaction conditions on the properties of the products was probed. Analysis of the prepared polymers was conducted using ¹H and ¹³C NMR, viscometry, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Viscometry values were generally found to be low, in the range of 0.175–0.300 dl/g. TGA showed losses starting at approximately 230°C and ending at 280°C, corresponding to the decomposition of the cyclopentadienyliron moiety. Degradation of the polyether backbone was found to occur starting at 390–567°C. Glass transition temperatures were found to be between 60 and 134°C, whereas melting temperatures ranged from 155 to 190°C.     

Bromine addition and successive amine substitution of mesoporous ethylenesilica: Reaction, characterizations and arsenate adsorption

Bromination and subsequent ethylenediamine substitution of the CC double bond in mesoporous ethylenesilica were carried out to explore the characteristics of this periodic mesoporous organosilica. The structures of the products (BrPMO and EDA–BrPMO, respectively) were analysed by IR, Br K-edge EXAFS and NMR spectroscopies, as well as X-ray diffraction and nitrogen adsorption. We showed (1) that the formulae of the two products that formed were [CHBrSiO_1.5]_0.45[CHSiO_1.5]_0.55 and [NH₂CH₂CH₂NHCHSiO_1.5]_0.05 [CHBrSiO_1.5]_0.40[CHSiO_1.5]_0.55, respectively, (2) that the addition of Br₂ at room temperature occurred on the CC double bonds with disturbing the framework structure, (3) that IR absorption band of CC bonds that reacted with Br₂ is significantly different from that of inactive CC bond, (4) that the length of the C–Br bond was considerably longer than in conventional alkyl bromides, and (5) that a large proportion of the ν(C–Br) band remained at the same position in the IR absorption spectrum after the ethylenediamine (EDA) substitution, while a new ν(C–Br) absorption also appeared. The mechanisms of these reactions are discussed at both the micro and mesoscopic levels.

Arsenate adsorption on EDA–BrPMO, in which the EDA is directly bound to the “surface” of the mesopores, was compared with adsorption on EDA–Pr–PMO, which was prepared by the direct synthesis of 3-chloropropyl-functionalized mesoporous ethanesilica followed by the substitution of Cl with EDA. The strength of the adsorption, as measured with the distribution coefficient, was greater for the former adsorbent than the latter. The origin of this difference was attributed to the distance between amino group and the surface.     

基于图像位平面分解的混沌加密方法研究

为提高图像加密效果,可结合混沌理论、位平面分解理论以及灰度置乱理论,获得一种加密新方法,即先对置乱后的图像进行位平面分解,再针对不同位平面使用不同的混沌加密密钥进行加密。仿真分析显示,此加密方法简单有效,密钥空间巨大,加密效果明显,安全性高。     

离子液体中均相合成N-乙酰化壳聚糖及其性能研究

合成了对壳聚糖溶解效果好、可重复使用的离子液体氯化2-氨基乙酸[Gly]Cl,用1H NMR和FT-IR对其结构进行了确定。在制得的离子液体水溶液中,制备了水溶性N-乙酰化壳聚糖。用XRD和FT-IR对产物进行了结构表征。通过单因素实验得到了较佳反应条件:n(乙酸酐)∶n(壳聚糖)=2.75∶1,反应温度60℃,反应时间5 h。并对产物的吸湿保湿性能进行初步研究,结果表明,产物具有良好的吸湿保温性能。还考察了离子液体的重复使用性能,重复使用3次后,N-乙酰化壳聚糖的取代度仍大于89%。     

改性纤维素增强丙烯酰胺水凝胶的合成与拉伸性能研究

采用水媒法制备了低取代度羧甲基纤维素,并用接枝聚合法制备了改性纤维素/丙烯酰胺水凝胶,考察了单体质量比、取代度等对水凝胶拉伸性能的影响.结果表明:对于接枝聚合反应,采用低取代度羧甲基纤维素可以提高纤维素的有效用量;当交联剂用量为180 mg/L、引发剂1 300 mg/L、低取代度羧甲基纤维素和丙烯酰胺质量比在1∶4 ～ 1∶4.5之间、单体质量分数为30%时,合成水凝胶的拉伸强度达到0.28 MPa;在此基础上,适量添加15%的淀粉可使水凝胶拉伸强度达到0.47 MPa;添加1%二氧化钛可使水凝胶拉伸强度达到0.38 MPa.     

Synthesis and Polymerization of Cationic bis(cyclopentadienyliron)arene Complexes Containing Arylazo Dyes

The synthesis of the title complexes was achieved via the reaction of -p-dichlorobenzene- -cyclopentadienyliron cations with 4,4′-bis(4-hydroxyphenyl)valeric acid to produce the diiron complexes which were then reacted with a number of arylazo dyes to give cationic bis(cyclopentadienyliron)arene complexes containing the arylazo dyes. These iron-containing monomers were subsequently polymerized via nucleophilic aromatic substitution using 1,8-octanedithiol, 4,4′-thiobisbenzenethiol, or bisphenol A to produce the desired coloured cationic organoiron polymers. The weight – average molecular weights were estimated to range from 11,800 to 31,600. UV–vis studies conducted in dimethylformamide (DMF) showed that the metallated polymers exhibited of 412–491 nm. Addition of HCl to the polymer solution caused a bathochromic shift into the range of 515–530 nm. Thermogravimetric analysis (TGA) revealed that the iron moieties were cleaved between 205 and 248 °C while the polyether/thioether backbone degraded between 380 and 613 °C. Differential scanning calorimetry (DSC) showed that the polymers exhibited glass transition temperatures (Tg) ranging from 106 to 184°C.This paper is dedicated to Professor Richard J. Puddephatt in recognition of his outstanding contribution to the field of metal-containing polymers.     

反映的规律为本构关系的变分原理

为证明经典变分原理中存在反映的规律为本构关系的变分原理,从非线性弹性动力学的基本方程出发,应用变积方法建立非线性弹性动力学Hamilton原理.再应用对合变换法、Lagrange乘子法和局部代入法,将Hamilton原理变换为本构变分原理.论证了该变分原理反映的规律为本构关系,本研究以非线性材料为例,找到了一个新的材料本构关系的获得途径,为数值建模提供了理论依据.研究结果表明,补充和完善了经典变分原理中对3类基本规律的反映,即:最小势能原理反映的规律为平衡关系、最小余能原理反映的规律为连续关系和本构变分原理反映的规律为本构关系.     

基于多素数和参数替换的改进RSA算法研究

为了提高RSA公钥算法在消息加密过程中的安全性,在深入分析传统RSA算法的基础上,对其进行一些改进性研究,提出了一种比传统RSA算法更加有效的方法优化其安全性。在将传统RSA改进为四素数RSA的基础上,再运用数学变换进行参数替换,消除了在公钥中对传输两个随机素数的乘积n的需要,引入了一个新的参数x代替原参数n。针对改进后的算法在运算效率方面的不足,采用中国剩余定理( Chinese remainder theorem,CRT)优化大数模幂运算。实验结果证实了改进算法的可行性,为通过公钥加密消息发送和接收提供了更安全的路径;同时,对改进算法与传统RSA 和四素数RSA算法的解密(签名)时间进行比较分析。实验结果表明改进后的算法对消息发送方和接收方之间签名效率也有一定程度的优化。