微量Mg/F表面梯度渗透改善高电压LiCoO2界面脆弱

采用高温固相法在1 050℃下烧结,制备了LiCoO₂低浓度梯度改性样品,分别为LiF掺杂包覆(LCOLF、LCO@LF)和MgF₂掺杂包覆(LCOMF、LCO@MF)。通过光电子能谱、透射电子显微镜和电化学技术等表征方法,对比分析材料形貌及电化学性能。结果表明,体相掺杂复合电极中,LCOLF热重测试显示出最优热稳定性,LCOMF晶体中(003)和(104)晶面间距收缩;45℃下1C倍率循环70圈后,LCOLF和LCOMF比容量分别为141.45和166.98 mAh·g^-1,循环性能优于LiCoO₂。表面包覆复合电极中,LCO@LF和LCO@MF晶粒表面光洁且晶格氧键价都向更高结合能方向增强;LCO@MF构建了坚实且紧密的包覆层,循环70圈后,放电比容量和容量保持率分别为183 mAh·g-1和91.26%(LCO@LF分别为154.38 mAh·g^-1和77.54%),循环性能显著优于体相掺杂。     

LiCoO2梯度包覆LiNi0.96Co0.04O2电极材料的电化学性能

镍钴酸锂(LiNi0.8Co0.2O2)与目前商业用锂离子电池正极材料钴酸锂(LiCoO2)相比,具有成本低、实际比容量高和环境友好等优势。但LiNi0.8Co0.2O2的充放循环性能还有待提高,对其进行阳离子掺杂或表面修饰可以改善其电化学性能,这方面的研究已经成为热点。Fey等人[1]用溶胶凝胶法制     

不同温度下合成的LiCoO2的晶体结构

研究了用Li₂CO₃和Co₃O₄固相合成锂离子电池正极材料钴酸锂(LiCoO₂)过程中，LiCoO₂的晶体结构随合成温度的变化。利用X射线衍射、扫描和透射电子显微技术等各种分析测试方法，对750～900 ℃范围内合成的LiCoO₂的形貌、晶体结构以及电化学性能进行了表征。实验证实，随着合成温度的增加，合成的LiCoO₂颗粒的形貌没有明显变化，但颗粒尺寸会增加；电子衍射结果表明，合成温度为800 ℃时可以合成Li、Co原子各自分层的六方晶体结构的LiCoO₂，随着合成温度的升高LiCoO₂中Li、Co原子层之间可能发生部分混合，合成温度为900 ℃时LiCoO₂为立方岩盐型晶体结构；800 ℃合成的LiCoO₂的充放电循环性能较好。     

Mg(BO2)2在MgCl2水溶液中的相平衡与化学平衡

借助拉曼光谱和X射线衍射(XRD)检测手段,对Mg(BO_2)_2在MgCl_2水溶液中水解的固液相平衡与物种化学平衡规律进行了研究。结果表明,MgCl_2对Mg(BO_2)_2的溶解转化、多硼氧配阴离子的物种分布有很大影响:(1)随着MgCl_2浓度从0达到饱和,Mg(BO_2)_2的表观饱和浓度从0.79%增加到1.96%,pH值从9.96降到6.27;(2)Mg(BO_2)_2在纯水中水解形成固相Mg_2B_6O_(11)·15H_2O和Mg(OH)_2,在MgCl_2溶液中形成固相Mg_2B_6O_(11)·15H_2O和Mg_3Cl_2(OH)_4·4H_2O;(3)Mg(BO_2)_2在纯水中水解,硼的物种主要为B_4O_5(OH)_4~(2-)和B_3O_3(OH)_4~-,分别占液相总硼含量的49.81%和19.54%。在MgCl_2饱和溶液中,主要为B_3O_3(OH)_4~-和B_5O_6OH)_4~-,分别占液相总硼含量的44.57%和40.00%。     

柠檬酸溶胶凝胶法制备LiCoO2电极材料及其表征

LiCoO₂ precursors of the cathode material for lithium-ion batteries were prepared from lithium hydroxide， basic cobalt carbonate and citric acid by a sol-gel method. The LiCoO₂ samples were obtained by sintering the gel pre-cursors at different temperatures and for different times. The thermal decomposition behavior of the gel precursors was examined by means of thermo-gravimetric analysis and differential thermal analysis using a PCT-IA thermal analyzer system. Their structures and morphologies were characterized by powder XRD and SEM techniques. It was found that using citric acid realized that the formation of LiCoO₂ crystal can be clearly differentiated to the nucle-ation and growth processes of the crystals; furthermore， the crystal size can be controlled. Electrochemical tests using the LAND BT1-10 test system showed the electrochemical performance of the material is affected by its in-tegrity and stability.     

超亲水TiO2和TiO2-SiO2表面的动态润湿性

1997年, Fujishima研究组[1]发现TiO2表面经UV光照射能产生较强的亲水性, 同时具有较高的亲油性, 即经UV光照射后的TiO2表面具有超双亲的性质. 这种防雾和自清洁性在工业上应用广泛, 已引起了人们的极大兴趣[2～5]. 进一步的研究发现, 超亲水的TiO2表面在暗处放置会变为疏水表面. 对于这个问题, 除了可以通过UV光照[6]、氩离子或电子束溅射[6]和高温热处理[5]等恢复其超亲水性外, 还可以通过添加摩尔分数为10%～30%的SiO2有效地降低TiO2表面的接触角, 提高UV光诱导的超亲水表面在暗处的稳定性能[3]. 另外, 诱导TiO2的亲水性需要较强的UV线强度(如太阳光), 使它在室内应用受到限制. 为了在室内实现TiO2的自清洁功能, Watanabe等[4]发现在TiO2中添加WO3可使TiO2在室内的照明光下也能实现亲水性转变. 以上这些研究成果为TiO2在工业和生活上的实际应用提供了重要的科学依据. 然而, TiO2的防雾和自清洁功能的实现同时也受其动力学性质的制约.     

LiCoO2中锂离子固相扩散系数随循环次数的变化

The solid diffusion coefficient of lithium-ion in LiCoO₂ cathode material has been investigated by the capacity intermittent titration technique (CITT) at different voltages and at different charge/discharge cycles. By SEM, XRD and FTIR techniques, the structure of LiCoO₂ was studied before and after charge-discharge cycles, and the relationship between solid diffusion coefficient and crystal structure was further discussed. CITT results show that the value of Li⁺ solid diffusion coefficient of LiCoO₂ is about 10^-12 cm²·s^-1. During the whole charge-discharge cycles, the Li⁺ solid diffusion coefficient decreased within the voltage of 4.0～4.3 V, which is attributed to the change of the structure of LiCoO₂.     

LaF3表面修饰LiMn2O4的合成方法及电化学性能的研究

通过高温固相法制得尖晶石LiMn₂O₄,然后在通过简单易行的无水乙醇蒸干法包覆LaF₃来修饰LiMn₂O₄。利用XRD,SEM来表征LaF₃修饰的LiMn₂O₄的结构和形貌特征,并通过电化学测试研究LaF₃修饰LiMn₂O₄的高温和常温下的电化学性能,另外结合电化学阻抗谱（EIS）和循环伏安（CV）考察表面修饰的锰酸锂的循环阻抗和循环可逆性。结果显示：经LaF₃修饰过的LiMn₂O₄仍具有尖晶石结构,并且具有良好的电学性能。其中,以3wt%的修饰效果最好,常温循环100次和高温循环50次的循环保持率分别是91%和90%;而且,EIS和CV分别表明经LaF₃修饰的LiMn₂O₄的电荷传递阻抗明显减小,其循环可逆性也明显提高。     

梯度材料LiNi0.8Co0.2O2的合成与表征

The gradient composite LiNi_0.8Co_0.2O₂ was synthesized using spherical Ni(OH)₂ particle coated by a sol-gel containing cobalt and lithium. The precursor was examined by DSC-TG. The gradient composite was characterized by SEM, EDS, XPS, XRD and ICP-AES. The XPS, EDS and ICP-AES results show that content of cobalt in the surface is higher than in the center of the spherical particle of the gradient composite. The first discharge specific capacity of the gradient composite sintered at 700 ℃ is 187.3 mAh·g^-1.     

尖晶石LiMn2O4的改性研究

由于资源丰富、价格便宜、易制备、对环境无污染、可回收利用等优点,尖晶石型LiMn2O4成为锂离子二次电池中最有希望的正极材料[1~3]。然而,在高电压充、放电条件下,由于电极中锰的溶解和Jahn鄄Teller效应的发生,会造成LiMn2O4容量迅速衰减[4~6]。为了改善LiMn2O4的电化学性能,研究者主要通过优化合成条件及合成方法来控制产品的粒径分布与形貌,以利于锂离子的脱、嵌[7,8];用掺杂的方法以稳定其结构,抑制Jahn鄄Teller效应的发生[9,10];用表面修饰的方式来减少活性物质与电解液的直接接触从而降低Mn的溶解[11,12]。掺杂方面,Co3 不仅有…     

Ni-Mn共掺杂高电压钴酸锂锂离子电池正极材料

以金属硫酸盐为原料,NaOH和NH₃·H₂O为沉淀剂,用共沉淀法合成了Co_0.9Ni_0.05Mn_0.05(OH)前驱体,再进行配锂并通过高温固相法合成了Ni-Mn共掺杂高电压钴酸锂锂离子电池正极材料Li(Co_0.9Ni_0.05Mn_0.05)O₂。用X射线衍射(XRD)、扫描电镜(SEM)、 循环伏安(C-V)、交流阻抗(EIS)和充放电测试研究样品的晶体结构、形貌和电化学性能。结果表明Ni-Mn共掺杂正极材料Li(Co_0.9Ni_0.05Mn_0.05)O₂有优秀的电化学性能:在3.0~4.4 V和3.0~4.5 V区间,0.5C倍率下首次放电比容量分别为162 mAh·g^-1和187 mAh·g^-1,循环100次后容量保持率分别为94%和94%。     

Ni-Mn共掺杂高电压钴酸锂锂离子电池正极材料

以金属硫酸盐为原料,Na OH和NH3·H2O为沉淀剂,用共沉淀法合成了Co0.9Ni0.05Mn0.05(OH)前驱体,再进行配锂并通过高温固相法合成了Ni-Mn共掺杂高电压钴酸锂锂离子电池正极材料Li(Co0.9Ni0.05Mn0.05)O2。用X射线衍射(XRD)、扫描电镜(SEM)、循环伏安(C-V)、交流阻抗(EIS)和充放电测试研究样品的晶体结构、形貌和电化学性能。结果表明Ni-Mn共掺杂正极材料Li(Co0.9Ni0.05Mn0.05)O2有优秀的电化学性能:在3.0~4.4 V和3.0~4.5 V区间,0.5C倍率下首次放电比容量分别为162.5 m Ah·g-1和185 m Ah·g-1,循环100次后容量保持率分别为94.4%和93.7%。     

新合成方法制备的LiCoO2正极材料的结构和电化学性能研究

采用新合成方法制备了锂离子二次电池正极材料LiCoO₂。通过ICP-AES、XRD、SEM、电化学方法等测试分析了所合成材料的物理性质和电化学性能，并与商品LiCoO₂材料作了对比研究。同时分别以国产MCMB和石墨作负极活性物质、合成的LiCoO₂作正极活性物质做成锂离子电池，对其电化学性能进行了测试。实验结果表明，所合成的LiCoO₂材料的电化学性能优于其它两种商品LiCoO₂材料，其初始放电容量为155.0 mAh·g^-1，50次循环后的容量保持率达95.3%，而且以此为正极的锂离子电池也表现出优良的电化学性能。计时电位分析结果还表明，合成的材料在充放电循环过程中发生了三次相转变过程，但相变过程具有良好的可逆性。     

Single-crystal synthesis and structure refinement of the LiCoO2-LiAlO2 solid-solution compounds: LiAl0.32Co0.68O2 and LiAl0.71Co0.29O2

Single crystals of the LiCoO₂-LiAlO₂ solid solution compounds LiAl_0.32Co_0.68O₂ and LiAl_0.71Co_0.29O₂ were synthesized by a flux method using alumina crucibles. A single-crystal X-ray diffraction study confirmed the trigonal space group and the lattice parameters a=2.8056(11) Å, c=14.1079(15) Å, and c/a=5.028 for LiAl_0.32Co_0.68O₂, and a=2.8023(7) Å, c=14.184(4) Å, and c/a=5.061 for LiAl_0.71Co_0.29O₂. The crystal structures have been refined to the conventional values R=3.2% and wR=2.4% for LiAl_0.32Co_0.68O₂, and R=3.6% and wR=3.5% for LiAl_0.71Co_0.29O₂. The evidence of the location of Al atoms in the pseudotetragonal coordination (6c site), reported previously in LiAl_0.2Co_0.8O₂, could not be observed in the present electron density distribution maps in both LiAl_0.32Co_0.68O₂ and LiAl_0.71Co_0.29O₂. The octahedral distortion analysis indicated that the Al-substitution strongly affected the distortion of the LiO₆ octahedron in this solid-solution compound system, but hardly affected that of the (Al.Co)O₆ octahedron.     

Structure and electron density analysis of electrochemically and chemically delithiated LiCoO2 single crystals

Single crystals of Li_0.68CoO₂, Li_0.48CoO₂, and Li_0.35CoO₂ were successfully synthesized for the first time by means of electrochemical and chemical delithiation processes using LiCoO₂ single crystals as a parent compound. A single-crystal X-ray diffraction study confirmed the trigonal R3¯m space group and the hexagonal lattice parameters a=2.8107(5) Å, c=14.2235(6) Å, and c/a=5.060 for Li_0.68CoO₂; a=2.8090(15) Å, c=14.3890(17) Å, and c/a=5.122 for Li_0.48CoO₂; and a=2.8070(12) Å, c=14.4359(14) Å, and c/a=5.143 for Li_0.35CoO₂. The crystal structures were refined to the conventional values R=1.99% and wR=1.88% for Li_0.68CoO₂; R=2.40% and wR=2.58% for Li_0.48CoO₂; and R=2.63% and wR=2.56% for Li_0.35CoO₂. The oxygen-oxygen contact distance in the CoO₆ octahedron was determined to be shortened by the delithiation from 2.6180(9) Å in LiCoO₂ to 2.5385(15) Å in Li_0.35CoO₂. The electron density distributions of these Li_xCoO₂ crystals were analyzed by the maximum entropy method (MEM) using the present single-crystal X-ray diffraction data at 300 K. From the results of the single-crystal MEM, strong covalent bonding was clearly visible between the Co and O atoms, while no bonding was found around the Li atoms in these compounds. The gradual decrease in the electron density at the Li site upon delithiation could be precisely analyzed.     

Synthesis and characterization of MgF2 and KMgF3 nanorods

MgF₂ nanorods with diameters of 60-100 nm were synthesized by a microemulsion method. Subsequent hydrothermal reaction of as-synthesized MgF₂ nanorods and KF at 240°C for 3 days or 140°C for 7 days resulted in KMgF₃ nanorods, which retained the rod-like morphology of the source material MgF₂ in the reaction process. The morphology of as-synthesized MgF₂ strongly depended on the molar ratio between water and the surfactant CTAB and the concentration of CTAB.     

LiCoO2对LiMn2O4改性过程的研究

在LiCoO2、LiMn2O4、LiNiO2这三种锂离子电池正极材料中,尖晶石LiMn2O4由于具有价廉、对环境友好、使用安全的显著优点,被普遍认为是最有希望的新型正极材料。但该材料在高温下较快的容量衰减制约了其规模应用[1~3]。为改善LiMn2O4的高温性能,各国学者普遍采用掺杂法,即在制备L