锂离子蓄电池正极材料LiNi1-yCoyO2的研究

从材料的结构、合成、电化学性能、热稳定性和贮存性能几个方面综述了LiNi1-yCoyO2 材料近期的研究开发状况。LiNi1-yCoyO2 不仅具备了LiCoO2 的特性 (易合成、性能稳定 ) ,更兼有LiNiO2 的高比容量、低成本之优点。而且在充放电过程中LiNi1-yCoyO2 没有发生纯的LiNiO2 材料所经历的三次相变 ,因而具有较好的循环性能。同时LiNi1-yCoyO2的不可逆容量可以为负极SEI膜的形成提供Li源 ,从而减少正极的额外装载量。其它过渡金属离子对LiNi1-yCoyO2 的再掺杂 ,进一步改善了材料的稳定性。实践表明 ,以LiNi1-yCoyO2 为正极材料的锂离子蓄电池具有较好的综合性能     

锂离子蓄电池正极材料LiNi1-yCoyO2的合成及性能

采用球形氢氧化镍的生产工艺合成了Ni1-yCoy(OH) 2 (0≤y≤ 0 .5 )共沉淀前驱体 ,利用该前驱体和锂盐一同焙烧后得到系列LiNi1-yCoyO2 固溶体。该方法避免了共沉淀时胶体的生成 ,而且与普通高温固相产物相比 ,烧成后的Li Ni1-yCoyO2 产物不仅保持了前驱体的原有形貌 ,而且具有更优良的电化学性能。通过电化学性能测试、SEM及X射线衍射等分析方法 ,我们系统研究了不同Co含量对材料电化学性能、结构以及前驱体形貌的影响。随着Co含量的增加 ,材料粒度逐渐降低 ,颗粒形貌由球形变为不规则形状 ;并且LiNi1-yCoyO2 材料的充放电及不可逆容量、放电电压均随Co含量的增加而呈降低趋势。当 0 .10≤y≤ 0 .2 0时 ,材料比容量可达 190mAh/g以上 ,且循环性能最优     

Significantly enhanced oxygen transfer capacity by the oxygen delivery channels formed in the inverse spinel CuxMg2‐xMnyTi1‐yO4.0 particle

Particles containing Cu and Mn as oxygen transfer species in the development of alternative oxygen carriers for commercialized NiO‐based particles used in CH₄ chemical looping combustion were investigated in this study. To maximize their oxygen transfer capacity, divalent Cu and tetravalent Mn were maintained in their respective oxidation states, which resulted in their reduction capacities not being canceled by each other. To prevent abrasion and sintering caused by collision and aggregation between 2 metals at high temperatures, they were stably fixed in an Mg_1.0Ti_1.0O_3.0 ilmenite support. As the result, the Cu‐substituted particle transferred to a pseudobrookite Mg_1.0Ti_2.0O_5.0 structure, and the particles with Cu²⁺ and Mn⁴⁺ substituting Mg²⁺ and Ti⁴⁺, respectively, changed to an inverse spinel Mg_2.0Ti_1.0O_4.0 structure, and not an ilmenite structure. In the hydrogen temperature‐programmed reduction test, the reduction temperatures of the Cu and Mn ions in Cu_xMg_2‐xMn_yTi_1‐yO_4.0 particles were significantly lower by 200°C or higher than those in the particles containing only Cu or Mn. Furthermore, adsorption curves of CH₄ and CO were shifted to low temperatures, and the adsorption concentrations were greatly increased for Cu_xMg_2‐xMn_yTi_1‐yO_4.0. For the cycling test for the CH₄‐CO₂/air redox system, the oxygen transfer capacities in particles containing only Cu or Mn were 3.4% or 3.1%, respectively, but this increased to 9.4% in Cu_1.5Mg_0.5Mn_0.5Ti_0.5O_4.0. In Cu_xMg_2‐xMn_yTi_1‐yO_4.0, the Mn species was present in the tetravalent state, and it participated in the CH₄ combustion reaction with the Cu ion, resulting in improved oxygen transfer ability. Finally, this study demonstrated an important mechanism, in which the Cu²⁺ and Mn⁴⁺ ions were reduced while combusting CH₄, and the Mg²⁺ and Ti⁴⁺ transfer oxygen to the reduced Cu and Mn through the inverse spinel lattice of Cu_xMg_2‐xMn_yTi_1‐yO_4.0. All metal species were reduced to like a dominos in the reduction system, creating a regular oxygen delivery channel in the crystal during the CH₄‐CO₂/air redox reaction, and resulting in improved oxygen transfer capacity.     

Preparation and properties of LiCoyMnxNi1−x−yO2 as a cathode for lithium ion batteries

The preparation of LiCo_yMn_xNi_1−x−yO₂ from LiOH·H₂O, Ni(OH)₂ and γ-MnOOH in air was studied in detail. Single-phase LiCo_yMn_xNi_1−x−yO₂ (0y0.3 and x=0.2) is obtained by heating at 830–900°C. The optimum heating temperatures are 850°C for y=0–0.1 and 900°C for y=0.2–0.3. Excess lithium (1z1.11 for y=0.2) and the Co doping level (0.05y0.2) do not significantly affect the discharge capacity of Li_zCo_yMn_0.2Ni_0.8−yO₂. The doping of Co into LiMn_0.2Ni_0.8O₂ accelerates the oxidation of the transition metal ion, and suppresses partial cation mixing. Since the valence of the manganese ion in LiMn_0.2Ni_0.8O₂ is determined to be 4, the formation of a solid solution between LiCo_yNi_1−yO₂ and Li₂MnO₃ is confirmed.     

Li1+xCryMn2-yO4合成工艺对其结构和性能的影响

用固相法高温合成得到尖晶石Li1 +xCryMn2 -yO4作锂离子二次电池正极活性材料 ,研究了不同合成条件对Li1 +xCryMn2 -yO4结构的影响 ,电化学性能测试表明LiMn2 O4掺Cr后初次放电容量有所下降 ,但循环性能有较大提高。     

正极材料Li_xNi_(1-y)Co_yO_2的制备及其性能

通过固态反应制得固溶体ＬｉｘＮｉ１－ｙＣｏｙＯ２,Ｘ射线衍射分析表明产物为层状结构。研究了反应预处理方式、气氛、温度和时间等因素对合成的影响,并加以比较,优化制备条件。以ＬｉＯＨ、Ｎｉ（ＯＨ）２和Ｃｏ３Ｏ４作为原料,在氧气气氛及６００℃～９００℃的温度范围内,制备出３种化学计量物质ＬｉＮｉ０７Ｃｏ０３Ｏ２、ＬｉＮｉ０５Ｃｏ０５Ｏ２和ＬｉＮｉ０３Ｃｏ０７Ｏ２,作为锂离子电池的正极材料。合成粉末的物性被表征。电化学行为的研究表明,３种产物的电化学性能都比较好,充放电容量均接近ＬｉＣｏＯ２的充放电容量。     

水基流延成型制备Li1+x-yNb1-x-3yTix+4yO3微波介质陶瓷膜片的研究

以Li1 x-yNb1-x-3yTix 4yO3微波介质陶瓷为原料,聚乙烯醇水溶液为粘结剂,乙二醇为增塑剂,聚羧酸铵盐为分散剂,通过水基流延成型工艺制备出了微观结构均匀的陶瓷素坯膜.通过对陶瓷粉体Zeta电位的考察研究了在水溶液中的粉体表面的带电情况.对陶瓷浆料的流变性进行了研究,考察了分散剂对浆料粘度的影响.最后对成型后陶瓷膜片的微观结构进行了观察.结果表明,添加分散剂后,Li1 x-yNb1-x-3yTix 4yO3陶瓷粉体在水溶液中的等电点由pH 3移动到pH 2.4,并且粉体的Zeta电位有大幅度的提高.Li1 x-yNb1-x-3yTix 4yO3微波介质陶瓷水基流延成型浆料为典型的假塑性流体,并且不存在触变性,满足流延成型工艺的要求.当分散剂的添加量为0.2wt%时,浆料的粘度最低.扫描电镜观察表明,水基流延成型后陶瓷素坯膜的微观结构均匀.