锂离子电池复合正极材料xLiFePO4·yLi3V2(PO4)3的制备与性能研究

以FePO4·xH2O、V2O5、NH4H2PO4和Li2CO3为原料,以乙二酸为还原剂,在常温常压下经机械活化并还原嵌锂,形成无定形的5LiFePO4·Li3V2(PO4)3前驱体混合物,然后低温热处理合成出晶态的复合正极材料5LiFePO4·Li3V2(PO4)3.分别研究了复合材料的物相结构、形貌、电化学性能.SEM图像表明合成的材料粒径小、分布均匀,一次粒径为100～200nm.充放电测试结果表明,650℃烧结12h制得的复合正极材料5LiFePO4·Li3V2(PO4)3电化学性能优良,1C放电比容量高达158mAh/g,达到该复合材料的理论比容量(156.8mAh/g).复合材料具有良好的倍率性能和循环性能,在10C放电比容量高达114mAh/g,100次循环后容量几乎无衰减.循环伏安测试表明,复合材料的脱嵌锂性能优良,且明显优于单一的LiFePO4和Li3V2(PO4)3.     

LiFePO4的前驱体制备与性能

以Fe2(SO4)3、H3PO4和NH3·H2O为原料,采用控制结晶法制备了多孔的前驱体FePO4·xH2O.通过研究pH值和合成时间对前驱体的物相结构、成分、表面形貌、粒度、比表面积和振实密度的影响,发现在pH=2.1的条件下反应8h制备的前驱体性能最佳.将前驱体、Li2CO3及葡萄糖均匀混合,用碳热还原法合成了LiFePO4/C,结果表明,以pH=2.1时制备的前驱体为原料合成的LiFePO4/C在0.1C时的首次放电比容量为156mAh/g,其振实密度高达1.20g/cm3.     

聚乙二醇为碳源合成0.7LiFePO_4·0.3Li_3V_2(PO_4)_3/C复合正极材料及性能研究

以Li OH·H2O、Fe C2O4·2H2O、NH4VO3和NH4H2PO4为原料,分别以不同聚合度的聚乙二醇(PEG-200、PEG-600、PEG-1000、PEG-2000、PEG-6000)为碳源,通过高温固相法合成0.7Li Fe PO4·0.3Li3V2(PO4)3/C复合正极材料(LFVP/C)。用X射线衍射、拉曼光谱和扫描电镜对材料的结构和形貌进行了表征。充放电测试表明,在电压范围为2.0~4.3 V时,PEG-200为碳源的LFVP/C的复合正极材料具有较高的比容量、优良的循环性能和倍率特性。10C条件下其放电容量可以保持120 m Ah/g。     

球形NH4FePO4·H2O的制备

以柠檬酸铵作络合剂通过控制结晶法制备了的球形NH4FePO4·H2O,用扫描电镜观察了颗粒的形貌和分布.通过研究加料方式、反应温度、滴加速度、搅拌速度、反应物浓度等对颗粒形态的影响,得到了制备球形NH4FePO4·H2O的最佳工艺条件.     

不同锂源对LiFePO4正极材料性能的影响

分别以Li2CO3,LiCl为锂源与FeC2O4·2H2O和NH4H2PO4混合,常温机械活化后在惰性气氛中经高温烧结,合成出纯相LiFePO4正极材料.采用X射线衍射仪,扫描电镜和电化学测试等对样品进行了表征,考察了不同锂源及合成温度对LiFePO4的物理特性和电化学性能的影响.结果表明,以Li2CO3、LiCl为锂源均能合成出橄榄石型LiFePO4正极材料,但以LiCl为锂源合成的样品中含有Fe2P2O4、LiFe5O8等微量杂质;其中以Li2CO3为锂源在650℃下烧结12h合成的样品具有优良的电化学性能,室温下以0.1和1C倍率放电,首次放电比容量分别为153.9和126.5mAh/g,循环性能较好.     

不同原料对锂离子电池正极材料LiCo0.05Mn1.95O4的晶体结构及电化学性能的影响

采用高温固相法,用不同的Li(LiNO3、LiCO3、LiOH·H2O)和Mn源(CMD、MnCO3、Mn(Ac)2·4H2O、EMD)分别合成了LiCo0.05Mn1.95O4样品,并结合XRD、SEM和电化学性能测试等手段,研究了不同原料对锂离子电池正极材料LiCo0.05Mn1.95O4的晶体结构、外观形貌和电化学性能的影响.     

锂离子电池正极材料LiNi0.5Mn1.5O4的固相法制备及性能研究

以Ni(CH3COO)2·4H2O和Mn(CH3COO)2·4H2O为原料,分别在400、500℃分解3、7h得到镍锰复合氧化物前驱体,再与锂源Li2CO3混匀,在800℃煅烧12h,600℃退火24h得到LiNi0.5Mn1.5O4正极材料。XRD、SEM、EIS和恒流充放电测试结果表明,在400℃、7h制备的前驱体与Li2CO3合成的LiNi0.5Mn1.5O4性能最佳。室温下以0.1C倍率充放电,首次放电比容量达到141.5mAh/g,循环30次后容量保持率为98.55%;以1C倍率充放电,首次放电比容量为120.34mAh/g,循环30次后放电比容量为112.09mAh/g。     

纳米LiFePO4/C复合材料的制备和性能

以Fe(NO3)3·9H2O、H3PO4和稀氨水为原料,用控制结晶法制备FePO4·x H2O,研究了表面活性剂CTAB和PEG对FePO4·x H2O材料的影响。再以Li2CO3、蔗糖和高温烧结后的FePO4为原料用碳热还原法制备了纳米LiFePO4/C复合材料。用SEM、XRD、充放电测试、循环伏安测试等手段对该复合材料进行表征,研究其电化学性能。结果表明:添加表面活性剂制备的LiFePO4/C复合材料纳米颗粒呈球形且团聚减少,提高了材料的倍率性能和循环性能,其中添加CTAB制备的LiFePO4/C材料的颗粒最小、分散性较好,0.1C时的首次放电比容量为159.8 m Ah·g-1,10C倍率下比容量仍达到132.4 m Ah·g-1。     

共沉淀法制备球形磷酸亚铁铵

以FeSO4·7H2O、NH4H2PO4、NH3·H2O为原料,用共沉淀法合成了用于制备磷酸铁锂正极材料的前驱体磷酸亚铁铵(NH4FePO4),通过XRD、SEM、FTIR等测试手段对材料进行了表征.通过正交实验得到了最佳工艺条件.在该工艺条件下材料振实密度达到1.73g/cm3.     

锂离子电池正极材料LiNi0.5Mn1.5O4的固相法制备及性能研究

以Ni(CH3COO)2·4H2O和Mn(CH3COO)2·4H2O为原料,分别在400、500℃分解3、7h得到镍锰复合氧化物前驱体,再与锂源Li2CO3混 匀,在800℃煅 烧12h,600℃退 火24h得 到LiNi0.5Mn1.5O4正极材料。XRD、SEM、EIS和恒流充放电 测 试 结 果 表 明,在400℃、7h制 备 的 前 驱 体 与Li2CO3合成的LiNi0.5Mn1.5O4性能最佳。室温下以0.1C倍率充放电,首次放电比容量达到141.5mAh/g,循环30次后容量保持率为98.55%;以1C倍率充放电,首次放电比容量为120.34mAh/g,循环30次后放电比容量为112.09mAh/g。     

Superconducting and normal state properties of ErRh4B4 and LuRh4B4

Detailed heat capacity measurements of the ternary compounds ErRh₄B₄ and LuRh₄B₄ have been performed between 0.5 and 36 K and in magnetic fields up to 4 kG, yielding new information on crystal field effects in these materials and on the influence of externally applied magnetic fields on the coupled superconducting-ferromagnetic reentrant transition in ErRh₄B₄. Static magnetic susceptibility data on LuRh₄B₄ are presented which allow qualitative conclusions to be drawn regarding the magnitude of exchange enhancement and orbital paramagnetic effects in the RERh₄B₄ compounds. The electrical resistivity of ErRh₄B₄ has also been determined between 4 K and room temperature.This research was supported by the Department of Energy under Contract Number Ey-76-S-03-0034-PA227-3 (LDW, HBM, RWM, MBM) and by the National Science Foundation under Grant Number NSF/DMR77-08469 (DCJ). One of us (RWM) thanks the National Science Foundation for a postdoctoral fellowship.     

10Cr4Ni4Mo4V钢和Cr4Mo4V钢的特性与断裂行为

对１０Ｃｒ４Ｎｉ４Ｍｏ４Ｖ钢和Ｃｒ４Ｍｏ４Ｖ钢的特性与断裂行为进行了试验研究。结果表明,１０Ｃｒ４Ｎｉ４Ｍｏ４Ｖ钢经微氮渗碳热处理后,其表面硬度、残余应力、断裂韧性及裂纹扩展速率均优于Ｃｒ４Ｍｏ４Ｖ钢的。     

Nano-phases of NaBH4 and KBH4

Phase stability and chemical bonding of beta-NaBH4 and beta-KBH4 derived nano-structures and possible low energy surfaces of them from thin film geometry have been investigated using ab initio projected augmented plane wave method. Structural optimizations based on total energy calculations predicted that, for beta-NaBH4 and beta-KBH4 phases, the (011) and (101) surfaces are more stable among the possible low energy surfaces. The predicted critical size of the nano-cluster for beta-NaBH4 and beta-KBH4 is 1.35 and 1.8 nm, respectively. The corresponding critical diameter for the nano-whisker is 2.6 and 2.8 nm respectively for beta-NaBH4 and beta-KBH4. Structural optimization based on total energy calculations show that the bond distances in the surfaces of nano-whisker are found to be higher than that in the bulk material and the calculated H site energies and bond overlap population analysis suggesting that it is considerably easier to remove hydrogen from the surface of the clusters and nano-whiskers than that from the bulk crystals.     

Dielectric properties of Bi4(GeO4)3 and Bi4(SiO4)3

Dielectric constant, dielectric loss and conductivity of Bi₄(GeO₄)₃ and Bi₄(SiO₄)₃ single crystals have been measured as a function of frequency and in the temperature range from liquid nitrogen temperature to 400° C. The values of the static dielectric constant at room temperature are 16·4 and 13·7 for Bi₄(GeO₄)₃ and Bi₄(SiO₄)₃ respectively. The plots of log (σ) against reciprocal temperature at different frequencies of these crystals merge into a straight line beyond 250°C and the activation energies calculated in this region are found to be 0·95 eV and 1·2 eV for Bi₄(GeO₄)₃ and Bi₄(SiO₄)₃ respectively.     

Low-temperature magnetic properties of HoRh4B4

The low-temperature magnetic properties of HoRh₄B₄ have been studied by means of measurements of the magnetic susceptibility, magnetization, specific heat, thermal expansion, and magnetostriction. The ferromagnetic phase transition at T _M= 6.7 K shows almost ideal S = 1/2 mean field behavior in the specific heat. Crystal field effects due to the splitting of the J = 8 Hund's rule ground state of the Ho³⁺ ions result in Schottky anomalies in the specific heat and the thermal expansion and are also revealed in the low-field magnetic susceptibility and the magnetostriction. Information on the ground state doublet of the 4f electrons has been obtained from the nuclear contribution to the specific heat below 1 K and the high-field magnetization below T_M.This research was supported by the Schweizerische Nationalfonds zur Forderung der wissenschaftlichen Forschung (HRO), by the Department of Energy under Contract No. EY-76-S-03-0034-PA227-3 (LDW, MBM), and by the National Science Foundation under Grant No. NSF/DMR77-08469 (DCJ)     

Quaternary system Li2MoO4-Na2MoO4-CaMoO4-BaMoO4

The Li₂MoO₄-Na₂MoO₄-CaMoO₄-BaMoO₄ quaternary system was studied by differential thermal analysis and direct visual observation. Three invariant points, two peritectic and one eutectic, were located.     

Low-temperature magnetic behavior of HoRh4B4

Detailed measurements of the magnetization of HoRh₄B₄ and GdRh₄B₄ near the magnetic transition temperature are presented. In contrast to the ferromagnetic behavior of GdRh₄B₄, no spontaneous magnetization is found to develop below T _min HoRh₄B₄. This raises doubts about the nature of the magnetic order in that material as well as in DyRh₄B₄ and TbRh₄B₄. Anisotropy and time dependence of the magnetization are found in these last three compounds. The behavior of the very small remanent magnetization and of the paramagnetic susceptibility of HoRh₄B₄ is shown. These results point to a complex magnetic order, possibly helical or sinusoidal antiferromagnetism with a long wavelength.Partially supported by a grant from the Swiss National Science Foundation.Research in La Jolla supported by National Science Foundation Grant No. DMR77-08467.     

LiZnPO4-LnPO4体系离子导电性的研究

采用柠檬酸盐溶胶-凝胶法制备了低温相α-LiZnPO4和以LiZnPO4为基质稀土磷酸盐(LnPO4)掺杂的(LiZnPO4)1-x-(LnPO4)x(Ln3+=Nd3+、Sm3+、Er3+、X=0.1;Ln3+=La3+,X=0.1、0.2、0.4、0.6)的超细粉体并对它们进行DTA、TG和XRD的表征.讨论了室温下不同比例、不同稀土磷酸盐的掺杂对基质LiZnPO4离子导电率的影响.测试结果表明,LiZnPO4-LnPO4体系是由α-LiZnPO4和LnPO4两相组成;由于α-LiZnPO4烧结体的相对密度(d=58)极小,室温下样品几乎不显示导电性,而适量的非导电相LnPO4的掺入有助于提高烧结体的相对密度,增大体系的晶界电导率.