喷雾干燥法合成锂离子电池复合正极材料xLiFePO4.yLi3V2(PO4)3及性能研究

采用喷雾干燥和高温固相法合成了一系列xLiFePO4·yLi3 V2( PO4)3复合正极材料.电化学测试结果表明,0.95LiFePO4·0.05Li3 V2( PO4)3复合正极材料具有较高的比容量、优良的循环性能和倍率性能,在电压范围为2.0V～4.3V,0.1C,1C,5C条件下的放电容量分别为162.7,147.7和122.3 mAh·g-1.0.5LiFePO4·0.5Li3 V2(PO4)3和0.3LiFePO4·0.7Li3 V2 (PO4)3复合正极材料则表现出了良好的倍率性能,5C,10C充放电条件下容量保持率分别为:77％,73％,88％,82％.     

熔盐法合成LiMn_（1/3）Ni_（1/3）Co_（1/3）O_2及AA电池的电化学性能

以KCl为熔盐,采用熔盐法合成了锂离子电池正极材料LiMn1/3Ni1/3Co1/3O2,扫描电子显微镜（SEM）显示此方法制备产物具有较好的晶形,颗粒较均匀.XRD表征结果显示产物为层状结构,充放电测试结果显示出材料在3.6 V平台附近有较大的可逆容量.在900℃时保温8 h时合成的LiMn1/3Ni1/3Co1/3O2具有较好的电化学性能,制作成AA电池,在2.75～4.2 V之间进行充放电测试,在1 C倍率下放电,LiMn1/3Ni1/3Co1/3O2的初始放电容量可达132.9 mAh/g,循环50多次后容量仍为124.6 mAh/g,容量保持率为93.75﹪.     

Influences of Nd~（3＋） doping on structure and electrochemical performance of layered Li_（1.05）V_3O_8

Nd3+-doped Li1.05V3O8 was synthesized by liquid-state reactions combined calcination.The influences of Nd3+ doping on physical and electrochemical performances of Li1.05V3O8 were investigated using X-ray diffraction (XRD),cyclic voltammograms,a.c.impedance and galvanostatic charge-discharge tests,etc.Results indicated that Nd3+-doped products had well developed crystal structure of layered LiV3O8 and uniform particle size distribution.Nd3+ doping with a proper amount improved the initial discharge capacity,discharge voltage and ion conductivity of the cathode material to some extent.Nd3+ did not participate in the electrochemical reactions and was beneficial to stability of the crystal structure during cycling.     

铌掺杂对镍基正极材料LiNi0.8Co0.1Mn0.1O2电化学性能影响

解决镍基正极材料LiNi_0.8Co_0.1Mn_0.1O₂的电化学循环稳定性和高温循环性能是其产业化推广应用的关键。研究了掺杂铌改性高镍正极材料,优化材料的电化学性能,提升循环稳定性。首先以硫酸盐为原料,在N₂保护气氛下,采用共沉淀法合成三元球形Ni_0.8Co_0.1Mn_0.1（OH）₂前驱体,通过高温固相反应与LiOH·H₂O,Nb₂O₅合成Li（Ni_0.8Co_0.1Mn_0.1）_1-xNb_xO₂（x=0,0.01,0.02,0.03）系列正极材料。X射线衍射结果表明,Nb5+离子可少量进入正极材料晶格,并在正极材料表面形成化学稳定性好的Li₃NbO₄。当x=0.02时,在室温25 ℃,电压2.75~4.2 V,0.2 C倍率下首次放电比容量为172.9 mAh/g,100次循环后容量保持率为97.47%,在50 ℃,0.5 C倍率下循环20次容量基本不变,平均放电比容量为183.7 mAh/g,且该样品具有较好的倍率性能。      

Effects of SrO/Li2O/La2O3/Ta2O5/TiO2-coating on electrochemical performance of LiCoO2

Commercial cathode material (LiCoO2) was modified by coating with a thin layer of SrO/Li2O/La2O3/Ta2O5/TiO2 for improving its performance in lithium ion battery. The morphology and structure of the modified cathode material were characterized by scanning elec-tron microscopy (SEM) and X-ray diffraction (XRD). The performance including cycling stability, diffusion coefficient under different volt-age, C-rate discharge of the batteries with this modified cathode material was examined. The results showed that the battery with the coated cathode material could discharge at a large current density, and it possessed a stable cycle performance in the range from 3.0 V to 4.2 V. It was explained that the rate of Li ion diffusion increased in the batteries using SrO/Li2O/La2O3/Ta2O5/TiO2-coated LiCoO2 as the cathode and the coated layer could act as a fast ion conductor (Sr0.5La0.05Li0.35Ti0.5Ta0.5O3) and as a protecting shell to prevent LiCoO2 particles from be-ing attacked by the acidic electrolyte.     

氧化铁复合颜料表面包覆层结构的X射线光电子能谱研究

表面包覆无机膜是改善粒子性能的重要方式,实验在铁红超细微粒子中掺杂稀土元素Nd和SiO₂,形成氧化铁复合颜料,采用X射线光电子能谱(XPS)研究表面无机膜的成分、化学状态及其含量,推测Fe₂O₃复合颜料表面包覆无机膜及稀土掺杂涂层的情况。结果表明,根据O 1s和Fe 2p谱图分析Fe-O键反应弱,推知Fe₂O₃粒子表面包覆情况良好,根据Si 2p和Nd 3d、Nd 4d化学位移,推测Nd、Si原子可能进入Fe₂O₃晶格,取代了O、Fe原子,降低了Fe-O的比例,重新结合形成新键,使复合粒子表面形成Nd-O-Si键,稀土原子成功掺杂在Fe₂O₃粒子表面包覆的SiO₂无机膜中。因稀土元素且有丰富的谱线特征,使制备的颜料色彩效果更佳,提高了粒子的性能。     

氧化钕和氧化镨钕在大气中的吸水特性研究

研究了氧化钕和氧化镨钕的吸水特性及吸水稳定后物质的结构与形态表征,通过增重试验及增重稳定后物质的X射线衍射试验,讨论了氧化钕和氧化镨钕吸水的一般动力学过程,并分析了影响吸水速率的因素。研究表明,氧化钕和氧化镨钕的吸水过程为未反应核模型,Lageren准一级、HO准二级动力学方程仅能对其诱导期之后的某个阶段拟合较好。氧化镨钕明显异于氧化钕,吸水产物孔隙率减小,吸一定水后出现类似"饱和"的现象。     

纳/微结构Sn-C复合负极材料的制备及其充放电性能

采用非水溶液溶胶-凝胶法,并结合高温碳热还原法制备锂离子电池用高可逆容量的Sn-C复合负极材料,通过调节Sn源与炭源的比例及碳热还原过程中的升温制度来控制金属Sn的粒度和Sn-C复合材料的结构形态。借助XRD、EDS、SEM、循环伏安及恒流充放电测试对材料的物化性能进行表征。结果表明,当Sn源与C源质量比为80:20、还原温度为800℃时,纳米级金属Sn均匀紧密地分布在无定形热解炭基体中,形成良好的纳/微复合结构,此时复合材料性能相对最优;该复合材料在电流密度为100 mA/g,首次可逆比容量为637.9 mAh/g,循环30次后充电容量保持在372.5 mAh/g以上,第二次循环库伦效率达到97%以上。     

一些金属阳离子的掺杂对尖晶石LiMn2O4的结构和电化学性质的影响

介绍了Co、Cr、Ni、Cu、Al 5种金属元素的掺杂对尖晶石LiMn2 O4 的结构和 4V区电化学性质的影响 :探讨了掺杂元素增加尖晶石锂锰氧化物 4V区循环稳定性的机理 ;减少了尖晶石在电解液中的溶解量 ;抑制了John Teller效应的发生 ;增加了键强度 ,使得尖晶石结构更加牢固。讨论了掺杂对尖晶石高电位 (>4 5V)区容量的影响 :掺杂后的尖晶石锂锰氧化物仍保持尖晶石结构 ,但与未掺杂的尖晶石锂锰氧化物相比 ,它的晶胞常数减小 ,晶胞体积收缩 ;锰元素的平均化合价升高 ;4V区的初始容量减小 ;循环稳定性明显增加。除Al外 ,Co、Cr、Ni、Cu掺杂后的尖晶石锂锰氧化物均在高电位区有一定的放电容量 ,且随掺杂量的增加而增加。     

金属钕工业生产中氧化钕利用率的探讨

在氟化体系氧化物电解金属钕的工业产中,针对Ｍｄ２Ｏ３在熔盐中溶解度低的情况下,尤其是以氟酸铈矿提取的ｎｄ２Ｏ３为原料电解时易发生沉底现象时,采取调整熔盐配比和适当提高氧化钕利用率的方法,可改善金属钕产品的表面质量,防止熔盐夹杂,降低产品中的碳含量,并可达到减少炉渣（废旧溶盐）生成、稳定炉况生产和节能降耗的目的。     

氧化钨/碳纳米管膜复合负极的制备及其储锂性能

氧化钨(WO₃)因具有较高的理论比容量(693 mAh/g)已成为锂离子电池负极材料的有力候选者。但在电池充放电即锂离子脱/嵌入过程中WO₃会产生较大的体积变化,导致其放电比容量快速衰减,故对其循环稳定性研究仍是热点之一。文中采用水热法和喷涂法分别在碳纳米管膜(CMF)基底上成功合成了水热型-氧化钨/碳纳米管膜(H-WO₃/CMF)和喷涂型-氧化钨/碳纳米管膜(S-WO₃/CMF)复合电极。XRD测试结果显示H-WO₃/CMF和S-WO₃/CMF中的WO₃分别属于单斜相和六方相。将H-WO₃/CMF和S-WO₃/CMF分别组装成扣式电池进行电化学性能测试,结果表明H-WO₃/CMF的首次放电比容量高于S-WO₃/CMF。当H-WO₃/CMF以0.2 C倍率循环时,第1圈放电比容量达到635 mAh/g,循环50圈时放电比容量为510 mAh/g,仍有上升趋势; S-WO₃/CMF在0.2 C倍率下循环时,第1圈放电比容量仅为515 mAh/g,在后续循环过程中容量衰减较快。交流阻抗测试结果显示H-WO₃/CMF的导电性高于S-WO₃/CMF。研究结果表明:H-WO₃/CMF作为锂离子电池负极,有望提升WO₃的电化学稳定性。      

Physicochemical properties of a novel composite polymer electrolyte doped with vinyltrimethoxylsilane-modified nano-La2O3

Nano-La2O3 was modified with the vinyltrimethoxylsilane by hydrolysis and a novel poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) based composite polymer electrolyte doped with the modified nano-La2O3 was prepared by phase inversion method. The physicochemical properties were studied by SEM, FT-IR, XRD, TG and electrochemical methods. The results of FT-IR indicated that the nano-La2O3 was successfully modified with vinyltrimethoxylsilane. The XRD analysis showed that the incorporation of modified nano-La2O3 into the polymer electrolyte membranes could effectively reduce the crystallinity of PVDF-HFP, and the characterizations also suggested that thermal stability and electrochemical stability window could reach to 382°C and 5.1V, respectively; the reciprocal temperature dependence of ionic conductivity followed Vogel-Tamman-Fulcher (VTF) relation, ionic conductivity at room temperature was up to 3.5×10-3S/cm and lithium ions transference number was up to 0.42; the interfacial resistance increased at initial value about353Ω/cm2 and reached a steady value about 559Ω/cm2 after 5d storage at 30°C. The fabricated Li/As-prepared electrolytes/LiCoO2 coin cell showed excellent rate and cycle performances.     

V2O5碳热还原合成碳化钒粉末的反应过程

为了实现小批量连续化制备碳化钒粉末,以工业级V2O5和纳米炭黑为原料,利用碳热还原法,在常压下碳管炉中得到了V8C7。通过X射线衍射仪(XRD)、扫描电镜(SEM),分析了合成过程。结果表明:在较低的温度下,纳米炭黑将V2O5还原为VO2;随着合成温度的升高,还原为更低价的V2O3,但没有VO生成;接着发生碳化反应,生成VC1-x、V8C7,合成的各阶段相互重叠;在合成过程中,试样的显微组织因物相不同而有所不同,生成的钒氧化物为炭黑附着的颗粒状大团聚体,VC1-x粉末颗粒呈类球形,但大小不均匀;随着温度升高,合成的最终产物V8C7粉末颗粒呈球形或类球形,大小均匀,粒度为1μm左右;还原碳化过程中,产生的气体有CO、CO2。     

碳源对Li3V2(PO4)3正极材料性能的影响

采用高温碳热还原法在惰性气氛下合成单斜晶型Li3V2(PO4)3正极材料,考察活性炭、蔗糖和酚醛树脂等不同碳源对目标材料性能的影响。采用XRD、FE-SEM和电化学测试等手段对目标材料进行结构表征和性能测试。结果显示,以酚醛树脂作为碳源的正极材料具有优良的电化学性能,首次放电比容量达138 mA.h/g,到第10次循环容量降至122.9 mA.h/g。酚醛树脂作碳源能在加热的过程中固化交联成三维的网状结构,极有效地限制了粒子的进一步长大,材料粒径最小。     

具有核壳结构的高电压正极材料Li(Co_(0.9)Ni_(0.05)Mn_(0.05))O_2的制备与表征

以共沉淀法制备的Ni-Mn包覆Co_3O_4前驱体和Li_2CO_3为原料,通过高温固相法制得了具有核壳结构的锂电池正极材料Li(Co_(0.9)Ni_(0.05)Mn_(0.05))O_2.用扫描电镜(SEM)、X射线能谱仪(EDS)、X射线衍射(XRD)和充放电测试表征了样品的形貌、晶体结构和电化学性能.结果表明,所制备的核壳结构Li(Co_(0.9)Ni_(0.05)Mn_(0.05))O_2具有良好的电化学性能,在3.0~4.5 V和3.0~4.6 V,0.2 C下首次放电容量分别达到180.5 m A·h·g~(-1)和201.3 m A·h·g~(-1),在1 C下,循环50周后容量保持率分别为89.3%和63.3%.     

富集稀土磷酸溶液中稀土的萃取研究

研究了P204从富集稀土磷酸溶液中稀土元素钇、镧、钕的萃取行为,并考察了初始水相中P_2O_5浓度、萃取相比、萃取剂浓度、萃取时间对稀土萃取效果的影响。结果表明,低磷酸浓度、较大相比、较高萃取剂浓度和较长萃取时间有利于萃取稀土,并得到了萃取优化条件:初始水相中P_2O_5浓度10%、萃取相比V_0/V_1=3/1、萃取时间15min、P204浓度30%,在室温下萃取钇、镧、钕3种稀土,单级萃取率均可达到90%以上。     

Cu_2V_2O_7的合成及电化学性能

采用溶胶凝胶法制备了锂离子电池负极材料Cu2V2O7,分别用X射线衍射仪,电子扫描电镜对产物的结构和微观形貌进行表征。结果表明,合成产物纯度高,微粒形貌规整、表面光滑、粒径小。用其组装的电池经恒流充放电测试表明,样品初始放电比容量为682.8mAh/g,具有良好的循环性能。     

Effects of La2O3/Li2O/TiO2- Coating on Electrochemical Performance of LiCoO2 Cathode

Conventional cathode material （LiCoO2） was modified by coating with a thin layer of La2O3/Li2O/TiO2 for improving its performance for lithium ion battery. The morphology and structure of the modified cathode material was characterized by SEM, XRD, and Auger electron spectroscopy. The performance of the cells with the modified cathode material was examined, including the cycling stability, the diffusion coefficient under different voltages, and the C-rate discharge. The results showed that the cell composed of the coated cathode material discharged at a large current density, and possesses a stable cycle performance in the range from 3.0 to 4.4 V. It was explained that the rate of Li ion diffusion increased in the cell while using La2O3/Li2O/TiO2-coated LiCoO2 as the cathode and the coating layer may act as a faster ion conductor （La2O3/Li2O/TiO2）.     

正极材料LiNi0.8Mn0.2O2前驱体合成工艺的探究

成本低、性能稳定的无钴镍锰正极材料是目前的研究热点。采用共沉淀法制备Ni_0.8Mn_0.2(OH)₂前驱体, 用氨水作为络合剂, 探究了NH₃浓度对前驱体Ni_0.8Mn_0.2(OH)₂共沉淀的晶粒生长和形貌的影响, 以及对锂离子电池正极材料LiNi_0.8Mn_0.2O₂的晶体结构和电化学性能的影响。通过X射线衍射仪、扫描电镜、循环伏安测试、交流阻抗和电池充放电测试系统表征材料的结构、形貌和电化学性能。表征结果显示, 在0.1 C, 2.5~4.2 V化成条件下, 初始放电比容量为167 mAh/g, 充放电效率为96%。当氨水用量为45 mL时, 样品具有较优的循环性能, 在1 C倍率下, 2.5~4.2 V的电压测试范围内, 循环100次后, 放电比容量为139 mAh/g, 容量保持率为93.9%。在低倍率充放电条件下样品具有明显优于其他材料的电化学性能。      

Catalytic Synthesis of Tert-Butyl Acetate by Nd2O3/Al2O3-Nd2O3/ZnO

Nd2O3 was used to support Al2O3 and ZnO to prepare a supported solid base catalyst and investigate the effect of catalyst and reaction conditions on the synthesis of tert-butyl acetate. The composited oxide of Nd2O3/Al2O3-Nd2O3/ZnO exhibited excellent catalytic activity for the synthsis of tert-butyl acetate. The molar ratio of tert-butanol to acetic anhydride is 31, the catalyst in total amount of reactant nearly 0.5%, and reaction time 6 h. With the above conditions, yield of the reaction could reach to 65%. The structure of product were verified by the FT-IR, Element analysis, and MS, which proved that the product was tert-butyl acetate.