Mg掺杂对LiNi_(0.6)Co_(0.15)Mn_(0.25)O_2电化学性能的影响

以氢氧化钠为沉淀剂,氨水为络合剂,通过氢氧化物共沉淀法制得前驱体,然后高温煅烧,合成锂离子电池正极材料Li(Ni_(0.6)Co_(0.15)Mn_(0.25))_(1-x)Mg_xO_2(x=0、0.01、0.02、0.03和0.04)。通过XRD、循环伏安、电化学阻抗谱(EIS)和恒流充放电等测试,研究Mg掺杂对材料性能的影响。适量的Mg掺杂可降低材料阳离子混排度,提高材料的循环性能及倍率性能。Li(Ni_(0.6)Co_(0.15)Mn_(0.25))_(0.98)Mg_(0.02)O_2的电化学性能较好,以0.1 C在2.7~4.3 V循环,首次放电比容量高达190.9 mAh/g;1.0 C循环30次的容量保持率为90.07%。     

锰掺杂对LiNi0.7Co0.3O2结构和电化学性能的影响

用溶胶-凝胶法制备了LiNi0.7Co0.3-xMnxO2(0≤x≤0.15)的前驱体.用XRD、XPS、SEM和恒流充放电法对最终产物的结构和电化学性能进行了研究.随着锰含量的增加,产物的晶胞参数变大,层状结构的有序性减弱.当0.02≤x≤0.07时,LiNi0.7Co0.3-xMnxO2的首次放电比容量(175～189 mAh/g)与30次循环后的容量保持率(》92%)均优于空白样品LiNi0.7Co0.3O2(170 mAh/g,86%).LiNi0.7Co0.25Mn0.05O2的首次放电比容量(189 mAh/g)最高,30次循环后的容量保持率为94%.实验结果表明,少量锰的掺杂能有效地提高材料的循环稳定性和可逆容量.     

球形LiNi_(0.8)Co_(0.15)Al_(0.05)O_2正极材料的制备及其电化学性能

采用共沉淀-喷雾干燥法制备了锂离子电池球形Li Ni0.8Co0.15Al0.05O2正极材料,通过热重分析法(TG)、X射线衍射光谱法(XRD)、扫描电子显微镜法(SEM)和电化学测试对材料的晶体结构、形貌及电化学性能进行了测试和表征。结果表明材料具有良好的层状结构,球形颗粒粒径约10μm;在30℃下,2.5~4.3 V循环,以20 m A/g放电,首次比容量达186.3 m Ah/g,循环50次后容量保持率为84.1%。     

Preparation of SrBi2Ta2O9 ferroelectric thin film by rf magnetron sputtering

Abstract

SrBi₂Ta₂O₉ (SBT) thin films were deposited on 6-inch Pt/Ti/SiO₂/Si substrates by rf magnetron sputtering using a 12-inch ceramic SBT single target. It is found that several sputtering parameters such as argon (Ar) pressure and rf power were very effective to control the Bi content of SBT thin films which is essential for obtaining good ferroelectric properties.     

Dielectric properties of zinc titanate thin films prepared by Rf magnetron sputtering

Zinc titanate thin films of ~500 nm in thickness were synthesized by an RF magnetron sputtering using a sintered ceramic target. After annealing in temperature ranges of 300–800 °C, their phase transition and dielectric properties were investigated as a function of annealing temperature. Crystalline ZnTiO₃ phase was first detected at the annealing temperature of 500 °C within XRD detection limit though the sputtered film was mainly amorphous. ZnTiO₃ still remained as a main phase although the slight decomposition of ZnTiO₃ into Zn₂TiO₄ and TiO₂ occurred in association with the increase of annealing temperature. Dielectric properties were apparently improved with increase of annealing temperature and showed maximum value at 650 °C. Further higher temperature annealing caused inferior dielectric property. These results were explained in terms of the presence of TiO₂ (rutile) phase, resulting from the decomposition of ZnTiO₃ phase, and the morphology of the thin film.     

高镍三元正极材料LiNi0.8Co0.1Mn0.1O2的合成与电化学性能研究

采用高温固相法在不同条件下合成了一系列球形LiNi0.8Co0.1Mn0.1O2正极材料,并通过XRD、SEM、TEM、EDS等表征手段对其物相结构、形貌以及电化学性能进行了研究.结果表明,Li/Me(摩尔比)为1.07时合成的正极材料结晶良好,结构稳定,以0.2 C倍率在2.8～4.3 V电压范围内的首次放电比容量为200.4 mAh/g,首次充放电效率为86.7％,1 C放电比容量为189.5 mAh/g,50次循环之后的放电比容量为178.3 mAh/g,此时容量保持率高达94.1％.继续循环至100次比容量还有145.7 mAh/g,容量保持率为76.9％.     

正极材料LiNi1/3CO1/3Mn1/3O2包覆LiNi0.8Co0.15Al0.05O2的性能

以NiSO4·6H2O、CoSO4·7H2O、MnSO4·H2O、NH3·H2O及NaOH为原料,采用共沉淀方法在LiNi0.8 C00.15 Al0.05 (OH)2球形粒子表面包覆一层Ni1/3 Co1/3Mn1/3(OH)2三元材料前驱体,配锂后在750℃下、氧气气氛中焙烧12 h,合成复合层状材料Li[(Ni0.8 Co0.15Al0.05)0.97(Ni1/3Co1/3Mn1/3)0.03]O2.复合层状材料具有核壳结构,包覆壳层的厚度约为1μm.复合层状材料在2.8～4.3 V充放电,0.1C首次放电比容量为188.2 mAh/g;0.2 C循环100次的容量保持率为96.2％;在55℃下以0.2C循环100次,放电比容量保持在163.2 mAh/g.     

锂离子蓄电池材料LiNi0.7Co0.2Mn0.1O2的制备与性能

采用共沉淀-高温固相合成工艺,将20%(质量分数)的Co和10%(质量分数)的Mn同时掺入,成功地在空气气氛中合成出了层状结构的多元正极材料LiNi0.7Co0.2Mn0.1O2.循环伏安曲线的测试结果表明,Co和Mn的同时掺入抑制了LiNiO2充放电过程中的相变,提高了材料的循环性能.在0.2 C倍率下2.8～4.3 V电压区间内进行充放电测试,结果表明,850℃下处理得到的样品前10次容量几乎没有衰减,均在150 mAh/g左右,循环50次后容量仍然保持在140 mAh/g以上.将充电截止电位提高至4.4 V后,前10次的放电比容量可达170 mAh/g.     

高温固相法合成LiNi0.25Co0.5Mn0.25O2及其结构性能研究

采用高温固相法合成了层状LiNi0.25Co0.5Mn0.25O2正极材料。通过X射线衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)以及恒电流充放电测试,研究了LiNi0.25Co0.5Mn0.25O2材料的结构、形貌以及电化学性能。实验结果表明950℃7 h合成的样品具有最好的电化学性能,在0.1 C时2.5～4.3 V间,其首次充放电比容量分别为166.3 mAh/g和150 mAh/g,循环10周容量保持96%;XRD精修结果表明Li层中只有1.1%的位置被Ni所占据。     

温度对LiNi0.45Co0.15Mn0.4O2性能的影响

采用共沉淀法先合成出前驱体Ni0.45Co0.15Mn0.4(OH)2,然后将其与Li2CO3均匀混合后在三种温度下烧结制得正极材料LiNi0.45Co0.15Mn0.4O2。用XRD、SEM和电池测试仪研究了烧结温度对材料结构、形貌和电化学性能的影响。结果表明:材料合成的最佳温度为900℃,在900℃条件下合成的LiNi0.45Co0.15Mn0.4O2具有较好的层状结构和较高的电化学活性,首次放电容量超过130mAh/g,8个循环后,容量保持率为99.1%,而且颗粒形貌呈球形并大小均匀适中。     

Structural and electrical properties of Sb-doped p-type ZnO thin films fabricated by RF magnetron sputtering

We investigated the Sb-doping effects on ZnO thin film using RF (radio frequency) magnetron sputtering and RTA (rapid thermal annealing). The structural and electrical properties of the thin films were measured by X-ray diffraction, SEM (scanning electron microscope), and Hall effect measurement. Thin films were deposited at a high temperature of 800°C in order to improve the crystal quality and were annealed for a short time of only 3 min. The structural properties of undoped and Sb-doped films were considerably improved by increasing oxygen content in the Ar-O₂ gas mixture. Sb-doping also significantly decreased the electron concentration, making the films p-type. However, the crystallinity and surface roughness of the films degraded and the mobility decreased while increasing Sb-doping content, likely as a result of the formation of smaller grain size. From this study, we observed the transition to the p-type behavior at 1.5 at.% of Sb. The thin film deposited with this doping level showed a hole concentration of 4.412?×?10¹⁷ cm^?3 and thus is considered applicable to p-type ZnO thin film.     

Effect of fluorine doping on the properties of ZnO films deposited by radio frequency magnetron sputtering

ZnO films with varying fluorine content were prepared on Corning glass by radio frequency magnetron sputtering of ZnO target containing ZnF₂ at room temperature, and the compositional, electrical, optical, and structural properties of the as-grown films together with the vacuum-annealed films were investigated. The fluorine content in the fluorine doped ZnO (FZO) films increased almost linearly with increasing ZnF₂ content in sputter target, and the highest atomic concentration was 7.3%. Vacuum-annealing caused a slight reduction of fluorine content in the films. The resistivity of the as-grown FZO films deposited showed a typical valley-like behavior with respect to the fluorine content in film, i.e. having minimum resistivity at intermediate fluorine content. Despite high fluorine content in the FZO films, the carrier concentration remained below 1.2?×?10²⁰ cm^?3, leading to very low doping efficiency level. Upon vacuum-annealing, the resistivity of FZO films decreased substantially due to increase in both the carrier concentration and the Hall mobility. From the structural analysis made by X-ray diffraction study, it was shown that addition of small amount of fluorine enhanced the crystallinity of FZO films with (002) preferred orientation, and that large amount of fluorine addition yielded disruption of preferred orientation. It was also shown that doping of fluorine rendered a beneficial effect in reducing the absorption loss of ZnO films in visible range, thereby substantially enhancing the figure of merit.     

Synthesis and electrochemical properties of LiNi1/3Co1/3Mn1/3O2 cathode materials by electrospinning process

The nanofibers of the LiNi_1/3Co_1/3Mn_1/3O₂ were successfully synthesized from a metal oxide precursor by the electrospinning method. After calcination above 700?°C, the nanofibers of the LiNi_1/3Co_1/3Mn_1/3O₂ cathode material were obtained in oxygen and air atmosphere. The XRD patterns of all prepared powders showed a hexagonal ?? - NaFeO₂ structure (space group: R - 3?m, 166). The scanning electron microscope showed that all the synthesized samples were comprised of nanofibers with a diameter of 100?~?800?nm. Among the samples tested, the calcined LiNi_1/3Co_1/3Mn_1/3O₂ nanofibers in oxygen heating atmosphere showed a high charge and discharge capacity for the first cycle of 217.93 and 172.81 mAhg^?1, respectively.     

正极材料LiNi0.5Mn0.5O2的合成及其性能研究

用共沉淀法制备镍锰氢氧化物前驱体,并通过高温固相反应在800℃空气气氛下煅烧12h合成锂离子蓄电池正极材料LiNi0.5Mn0.5O2,研究了冷却速度和升温制度对材料电化学性能的影响。结果表明,在500℃预处理5h,800℃煅烧完毕立即从炉中取出,环境温度下在空气中冷却,得到的样品比容量能达到180mAh·g-1,材料在2.5～4.6V范围内循环时性能不佳,当采用恒流/恒压模式,在2.5～4.3V范围内,材料具有良好的循环性能。     

无钴镍基正极材料LiNi_(0.8)Mn_(0.2)O_2的制备及电化学性能研究

采用共沉淀法合成球形前驱体Ni_(0.8)Mn_(0.2)(OH)_2,混合LiOH·H_2O通过高温烧结制备出锂离子电池镍基正极材料LiNi_(0.8)Mn_(0.2)O_2。通过X射线衍射(XRD)、扫描电镜(SEM)、热重-差热分析(TG-DTA)以及恒电流充放电测试对材料进行表征,研究了烧结温度和烧结气氛对材料结构、形貌和电化学性能的影响。结果表明:800℃纯氧气氛(0.6L/min)下煅烧12h合成的材料晶型完整,是典型的六方晶系α-NaFeO_2型结构;SEM测试显示材料平均粒径在10μm左右;电化学性能测试显示材料在25℃、2.75~4.20V、0.2C充放电条件下,首次放电比容量达173.6mAh/g,循环95次后,容量保持率达90.73%。     

合成时间对LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2结构与电化学性能的影响

采用球形Ni0.5Co0.2Mn0.3(OH)2前驱体与Li2CO3混合,通过高温烧结合成层状Li Ni0.5Co0.2Mn0.3O2正极材料,研究了合成时间对材料结构及电化学性能的影响。扫描电子显微镜法(SEM)表明Li Ni0.5Co0.2Mn0.3O2正极材料与前驱体形貌均为理想的球形。X射线衍射光谱法(XRD)分析表明,在不同合成时间下合成的样品均为具有层状结构的纯相物质。电化学性能测试表明,900℃12 h合成的样品具有最优的电化学性能,在2.7~4.4 V电压区间,0.1 C、1 C、5 C的首次放电比容量分别达到195.2、158.4和114.9 m Ah/g,1 C循环10次容量保持率为98.9%。     

高性能LiNi0.7Co0.1Mn0.2O2正极材料合成工艺及电化学性能研究

通过化学共沉淀和高温固相反应法合成不同Li/M比(Li为锂元素的物质的量,M为过渡金属元素总物质的量)的LiNi0.7Co0.1Mn0.2O2正极材料,采用XRD、SEM、恒流充放电测试系统和电化学工作站研究Li/M比对材料结构、形貌和电化学性能的影响。结果表明,Li/M比为1.10的LiNi0.7Co0.1Mn0.2O2正极材料层状结构完整,颗粒形貌良好,电化学性能最优。0.2 C充放电条件下的首次放电比容量达到204.0 mAh/g;1.0 C充放电条件下循环充放50圈后放电比容量为187.0 mAh/g,容量保持率达到97.2%。     

LiMn2O4薄膜的溶胶-凝胶法制备及其电化学性质

以醋酸锂、醋酸锰、乙二醇甲醚和乙酰丙酮为原料,采用溶胶 凝胶法制备薄膜锂离子蓄电池正极材料尖晶石LiMn2O4薄膜。用X射线衍射、扫描电镜分析了薄膜的物相和表面形貌,用循环伏安法、充放电和交流阻抗技术研究了薄膜的电化学性能。结果表明该法制备的LiMn2O4薄膜均匀、无开裂,750℃退火5min得到的薄膜的首次放电容量为36μAh/(cm2·μm),经100次循环后每次循环的容量损失为0.037%,薄膜具有良好的电化学性能。     

高电压型纳米Al_2O_3包覆LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2的制备和电化学性能

利用溶胶-凝胶法在LiNi1/3Co1/3Mn1/3O2颗粒表面包覆一层纳米级厚度的Al2O3,提高了其高截止电压下的循环性能和倍率性能。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜法(TEM)对所制备材料进行结构和微观形貌表征,通过充放电测试对材料的电化学性能进行分析。结果表明:Al2O3包覆层对材料的结构和微观形貌没有影响;Al2O3的最佳包覆量为2.0%(质量分数),此时包覆层的厚度为20~30 nm。在2.8~4.5 V电压范围内,未包覆的LiNi1/3Co1/3Mn1/3O2在0.2 C时的首次放电比容量为175 m Ah/g,50次循环后容量保持率只有91.8%;经Al2O3包覆的LiNi1/3Co1/3Mn1/3O2在0.2 C下,首次放电比容量达到181 m Ah/g,经50次循环后容量保持率仍可达到97.4%,且在5 C放电条件下,其放电比容量可达152 m Ah/g,显示了该包覆材料在高能量密度长寿命锂离子电池中将具有很大的应用潜力。     

氢氧化物前驱体制备LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2的机理

用共沉淀法制备前驱体Ni0.5Co0.2Mn0.3(OH)2,焙烧前驱体与Li2CO3制备Li Ni0.5Co0.2Mn0.3O2。用XRD、SEM和DSCTGA分析焙烧中间产物的结构、形貌及变化,探索制备Li Ni0.5Co0.2Mn0.3O2的机理。随着焙烧温度的升高,前驱体分解成(Ni0.5Co0.2Mn0.3)3O4,随后Li2CO3参与反应,形成Li Ni0.5Co0.2Mn0.3O2。Li Ni0.5Co0.2Mn0.3O2的生成在650℃时结束,但层状结构在900℃时才趋于完美。