Li_(1.02)Mn_(1.92)Al_(0.02)Cr_(0.02)Mg_(0.02)O_(4-x)F_x尖晶石正极材料的研究

采用溶胶-凝胶法合成了复合离子掺杂的尖晶石型锰酸锂Li1.02Mn1.92Al0.02Cr0.02Mg0.02O4-xFx(x=0,0.06)正极材料,并用XRD、CV、EIS和充放电测试等研究了其结构和电化学性能。结果表明,F与金属离子(Li、Al、Cr、Mg)的复合掺杂不仅提高了材料的比容量,还增加了尖晶石结构的稳定性,改善了材料的循环性能和可逆性能;充放电测试结果表明,Li1.02Mn1.92Al0.02Cr0.02Mg0.02O3.94F0.06具有优越的循环性能,常温下,以1/3C充放电的首次放电容量及50个循环后的容量保持率分别为117.9 mAh/g,96.9%。     

熔盐燃烧合成LiNi_(0.01)Cr_xMn_(1.99-x)O_4(x≤0.07)正极材料及电化学性能

采用熔盐燃烧法制备Ni和Cr共掺杂尖晶石LiNi_(0.01)Cr_xMn_(1.99-x)O_4(掺杂Cr的量x≤0.07)正极材料,以改善锂离子电池正极材料的电化学性能。通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等对其晶体结构、微观形貌和物相组成进行表征,并利用恒电流充放电测试、循环伏安(CV)和电化学阻抗谱(EIS)对电化学性能进行研究。结果表明,样品均为单相尖晶石LiMn_2O_4结构,颗粒尺寸在50～100 nm。x=0.05样品具有高的Li~+扩散系数和低的电荷转移电阻,表现出优良的动力学性能和电化学性能。在1 C,x=0.05样品首次放电比容量为114.3m A×h×g~(-1),循环500次后的容量保持率为74.8%,即使在20和30 C的较高倍率,经过1 000次长循环后,仍分别保持51.9%和43.1%的容量保持率。适量的Ni-Cr共掺杂提高了LiMn2O4的晶体结构稳定性,改善了电化学性能。     

Ni-Co复合掺杂LiMn2-2xNixCoxO4的合成与性能研究

为了改善锂离子电池正极材料LiMn2O4的循环性能,对Ni-Co复合掺杂LiMn2O4的合成与性能进行了研究.溶胶-凝胶法合成的LiMn2O4试样为纯的立方尖晶石相,且结晶状态良好.Ni-Co复合掺杂综合了Ni掺杂效应和Co掺杂效应,不仅提高了材料的初始放电容量,而且改善了材料的电化学性能.在3.0V-4.3V充放电压范围内,初始容量达到139mAh/g,36次循环后容量仅仅衰减3.6%.     

掺杂Zr~(4+)对LiMn_2O_4性能的影响

采用高温固相反应法,用ZrO2掺杂尖晶石L iMn2O4,制得了具有完整尖晶石结构的锂离子电池正极材料L iMn2-xZrxO4(x=0-0.02)。对材料进行了测试,试验结果表明,掺杂了微量Zr4+制得的正极材料,经100次充放电循环后材料比容量为102 mAh/g。采用不同充放电倍率进行充放电测试,随着充放电电流的增大,材料容量相应降低。     

锰酸锂的制备及其在中性电解液中的电容性能

用高温固相法合成尖晶石型锰酸锂(LiMn2O4)电极材料.X射线衍射结果表明:800 ℃下得到纯的尖晶石型LiMn2O4样品.利用恒流充放电、循环伏安和交流阻抗等测试方法研究LiMn2O4在2 mol/L(NH4)2SO4溶液中的电容性能.结果表明:LiMn2O4电极材料在中性电解液中有较好的电容性能,电极的充放电曲线基本呈线性关系,比容量可达90F/g.电极经500次循环后容量并无衰减,具有极好稳定性.交流阻抗结果显示:LiMn2O4电极材料在2mol/L(NH4)2SO4溶液中内阻仅为0.3Ω.     

掺杂型尖晶石Li_(1.05)Mg_xMn_(2-x)O_4的合成及性能研究

采用高温固相法制备了尖晶石正极材料L iMxMn2-xO4(X=0.04,0.06,0.08,0.10),并用XRD、SEM、ICP-AES、充放电测试等手段研究了其组成、结构、表观形貌和电化学性能。结果表明:该法制备的尖晶石正极材料L iMxMn2-xO4为单一尖晶石结构,粒径分布均匀,其比容量和循环性能较未掺杂尖晶石L iMn2O4有显著的提高。     

二元掺杂尖晶石LiMn2O4的合成与性能研究

采用高温固相法合成了二元掺杂改性的尖晶石型锰酸锂正极材料LiMn1 97Co0.02M0.01O4(M=La,Zr,Cr,Al,Ni).用X射线衍射法对材料进行了表征,表明所得材料均呈完美的尖晶石结构.通过充放电测试,发现掺杂后的材料循环性能有很大程度的改善.其中LiMn1.97Co0.02La0.01 O4具有较高的放电容量,同时循环50次后仍保持首次放电容量的92.4%.     

溶胶-碳热法制备LiM_xFe_(1-x)PO_4/C〔M=Mg,Ni;x=0.06〕及其电化学性能研究

采用溶胶-碳热法制备Li MxFe1-xPO4/C〔M=Mg,Ni;x=0,0.06〕复合正极材料,通过XRD、SEM、恒流充放电和循环伏安等测试方法研究了Mg和Ni掺杂对材料结构,形貌和电化学性能的影响。结果表明:Mg和Ni的适量掺杂并未改变材料的结构和形貌,但材料的充放电性能、循环稳定性和可逆性明显提升。Li Ni0.06Fe0.94PO4/C的比容量、容量保持率均优于Li Mg0.06Fe0.94PO4/C。     

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%。     

尖晶石型LiMn2O4正极材料的最新研究进展

尖晶石型锰酸锂以成本低廉、资源丰富和良好的安全性能,成为动力锂离子电池的理想正极材料。但尖晶石LiMn2O4高温循环性能差限制了其应用。阐述了尖晶石LiMn2O4容量衰减的机理;详细介绍了国内外在LiMn2O4正极材料体相掺杂和表面包覆改性的研究进展,并对体相掺杂和表面包覆改性LiMn2O4正极材料电化学性能提高的机理进行了讨论。最后对尖晶石LiMn2O4正极材料今后的发展方向进行了展望。     

Ferroelectric Ceramics in the PbMg1/3Nb2/3O3-PbCd1/3Nb2/3O3 System

Solid solutions (1-x)PbMg_1/3Nb_2/3O₃ + xPbCd_1/3Nb_2/3O₃ with x = 0-0.30 are investigated with purpose to work out a capacitor ceramics with good dielectric properties and low sintering temperature. It is found that the perovskite phase forms at sintering near to 980°C and begins to decompose at higher temperatures. When x grows from 0 to 0.30, the Curie temperature linearly grows from -10°C to +25°C, the dielectric permittivity ε_m in the Curie point T_C decreases from 18000 to 6800 and the phase transition becomes more diffused. The dielectric permittivity at room temperature is rather high and the temperature stability is improved. The system is of interest, because it can serve as a base for working out some ceramic materials for capacitors with low sintering temperature, which needs of no special atmosphere at burning.     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇（BBMP）为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷（BrMMO）。讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响。通过实验确定的最佳工艺条件为：BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4h时,BrMMO产率为65%。最终产品经元素分析、IR和1HNMR检测确定为BrMMO。该试验工艺简单,原料易得,且溶剂便于回收、污染小。     

3-叠氮甲基-3-甲基氧丁环的合成

以三羟甲基乙烷与碳酸二乙酯为原料,经环化反应合成了3-羟甲基-3-甲基氧丁环(HMM O)。在低温下,HMM O与对甲苯磺酰氯反应生成3-磺酸酯甲基-3-甲基氧丁环(M TM O)。M TM O和叠氮化钠发生叠氮化反应形成叠氮单体3-叠氮甲基-3-甲基氧丁环(AMM O)。三步反应收率分别为76%,96%,85%。用核磁、红外、元素分析和DSC表征了化合物的结构与性能。结构鉴定表明为目标化合物AMM O。     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇(BBMP)为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷(BrMMO).讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响.通过实验确定的最佳工艺条件为:BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4 h时,BrMMO产率为65%.最终产品经元素分析、IR和1HNMR检测确定为BrMMO.该试验工艺简单,原料易得,且溶剂便于回收、污染小.     

The Preparation and Crystal Structure of TlMnCl3, TlFeCl3, TlCoCl3 and TlNiCl3

The compounds TlMnCl₃, TlFeCl₃, TlCoCl₃ and TlNiCl₃ were prepared by heating T1C1 with the corresponding transition metal dichloride in an evacuated ampoule. Atomic positions were determined from powder photographs. All four compounds were found to be related to the perovskite type structure. TlMnCl₃ has a cubic structure, space group Pm3m, with a_o = 5.025 Å. The other three compounds are hexagonal, probable space group P6₃mc, with cell dimensions (in Å) a₀ = 6.976 and c₀ = 6.008 for the Fe compound, a₀ = 6.907 and c₀ = 5.981 for the Co compound and a₀ = 6.863 and c₀ = 5.881 for the Ni compound. The three hexagonal compounds are isomorphous. A measureable concentration of basal plane stacking faults was found to occur in TlFeCl₃ and also, to a lesser degree, in TlCoCl_3.     

Tunable color emission in LaScO3:Bi3+,Tb3+,Eu3+ phosphor

LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ (x = 0 − 0.04, y = 0 − 0.05, z = 0 − 0.05) phosphors were prepared via high-temperature solid-state reaction. Phase identification and crystal structures of the LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors were investigated by X-ray diffraction (XRD). Crystal structure of phosphors was analyzed by Rietveld refinement and transmission electron microscopy (TEM). The luminescent performance of these trichromatic phosphors is investigated by diffuse reflection spectra and photoluminescence. The phenomenon of energy transfer from Bi³⁺ and Tb³⁺ to Eu³⁺ in LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors was investigated. By changing the ratio of x, y, and z, trichromatic can be obtained in the LaScO₃ host, including red, green, and blue emission with peak centered at 613, 544, and 428 nm, respectively. Therefore, two kinds of white light-emitting phosphors were obtained, LaScO₃:0.02Bi³⁺,0.05Tb³⁺,zEu³⁺ and LaScO₃:0.02Bi³⁺,0.03Eu³⁺,yTb³⁺. The energy transfer was characterized by decay times of the LaScO₃:xBi³⁺, yTb³⁺, zEu³⁺ phosphors. Moreover absolute internal QY and CIE chromatic coordinates are shown. The potential optical thermometry application of LaScO₃:Bi³⁺,Eu³⁺ was based on the temperature sensitivity of the fluorescence intensity ratio (FIR). The maximum S_a and S_r are 0.118 K⁻¹ (at 473.15 K) and 0.795% K⁻¹ (at 448.15 K), respectively. Hence, the LaScO₃:Bi³⁺,Eu³⁺ phosphor is a good material for optical temperature sensing.     

2,2,3-三氯-3-苯基-3-(3-甲基苯甲酰基)丙腈的合成研究

以苯甲酰氯、四氯化碳、间甲基苯甲酰氰为原料,合成了标题化合物。重点考察了氰化过程中不同原料配比、反应温度、时间、溶剂和催化剂用量对收率的影响。实验结果表明,其最佳反应条件为:n(1,1,2-三氯-2-苯基乙烯)∶n(3-甲基苯甲酰氰)=1∶1.2,二氯甲烷为反应溶剂,3 mmol催化剂三乙胺,室温反应5 h,总收率达80.6%。     

Thermal analyses of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by T_o = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was T_p = 0.91B + 320, and the temperature at which degradation was completed was T_f = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), T_o = 0.96B + 308, T_p = 0.99B + 320, and T_f = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), T_o = 1.11B + 305, T_p = 1.10B + 319, and T_f = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures T_o, T_p, and T_f relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001