层状Lix[Mn1-yCoy]O2正极材料的合成及电化学性能研究

采用柠檬酸溶胶凝胶法合成了钠锰青铜Nax[Mn1-yCoy]O2,其中Nax[Mn1-yCoy]O2(0.3≤y≤0.5)具有理想的层状P2结构;以P2结构的Nax[Mn1-yCoy]O2为前驱体,离子交换后得到O2结构产物Lix[Mn1-yCoy]O2,并进行了XRD,ICP和电化学性能研究,结果表明不同Mn/Co投料比对前驱体中Nax[Mn1-yCoy]O2的结构有较大的影响,并且不同的离子交换方法对产物Lix[Mn1-yCoy]O2的结构和组成有较大的影响。对Li0.9Mn0.7Co0.3O2在充放电电压为2.6-4.5V(vs.Li /Li),电流密度为0.2mA/cm2的充放电条件下进行电化学测试后发现,该材料的首次充放电容量达152.70mAh/g,且循环性能良好。     

共沉淀法制备Li[Li0.1 Ni0.45-xMn0.45-xSn2x]O2微米球及其电化学性能研究

目的:制备正极材料Li[Li_0.1Ni_(0.45-x)Mn_(0.45-x)Sn_2x]O_2微米球,并研究其电化学性能与掺杂Sn^2+的物质的量的关系。方法:通过共沉淀法以SnSO_4、Na_2CO_3、MnSO_4?H_2O和NiSO_4?6H_2O为原料,制备前驱物(Ni_(0.45-x)Mn_(0.45-x)Sn_2x)(CO_3)_0.9,与Li_2CO_3充分混合,高温煅烧得到正极材料Li[Li_0.1Ni_(0.45-x)Mn_(0.45-x)Sn_2x]O_2微米球。结果:正极材料的物相用X射线衍射（XRD）进行检测,表观形貌利用扫描电子显微镜（SEM）进行研究,采用恒流充放电测试对电池电化学性能进行分析。结论:添加Sn^2+可以有效提高Li[Li_0.1Ni_(0.45-x)Mn_(0.45-x)Sn_2x]O_2系列锂离子正极材料的电化学性能。     

Li[Li(1/3-x/3)Mn(2/3-2x/3)Cox]O2(x=O.1)的团簇自旋玻璃态行为

采用柠檬酸盐法制备了六方层状结构的Li[Li(1/3-x/3)Mn(2/3-2x/3)Cox]O2(x=0.1)材料.体系在高温区呈现顺磁态,通过拟合Curie-Weiss定律得到Curie和Weiss常数分别为1.70(2)m3 K/mol和-22(3)K.该材料的磁化率曲线在低温区表现出不可逆转变行为,并且这种不可...     

Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2富锂正极材料表面修饰LaF_3及其电化学性能的研究

采用溶胶凝胶方法合成Li[Li0.2Mn0.54Ni0.13Co0.13]O2富锂正极材料,通过化学沉积技术在Li[Li0.2Mn0.54Ni0.13Co0.13]O2颗粒表面沉积La F3颗粒.利用X-射线衍射(XRD)、扫描电子显微镜(SEM)、充放电测试、循环伏安及交流阻抗测试系统研究了La F3包覆对材料电化学性能的影响.合成的材料具有α-Na Fe O2层状结构且La F3颗粒均匀包覆在颗粒表面,表面修饰La F3后的样品表现出更高的比容量和更好的倍率性能,电化学性能测试表明La F3表面修饰层有助于缓解电解液中HF对活性材料的腐蚀,降低电荷跃迁电阻(Rct),增强锂离子的扩散能力.     

共沉淀及高温固相法合成LiaNi0.6Co0.4O2及其电化学性能研究

采用共沉淀方法合成出具有较高活性的前驱氢氧化物,经预处理后再用高温固相法合成Li aNi0.6Co0.4O2(1＜a＜1.05)正极材料,其结晶良好,结构发育较完善.样品经XRD,SEM和充放电性能测试说明层状结构稳定,首次放电容量为156.0 mAh·g-1,充放电40次后仍有 146.0 mAh·g-1,放电容量损失仅为6.4%.     

新型锂离子电池正极材料Li3V2(PO4)3的研究进展

Li3V2(PO4)3是当今较新型的锂离子电池正极材料之一,其显著优点之一是在大容量动力锂离子电池研发方面拥有巨大的应用潜力.研究表明,Li3V2(PO4)3跟LiCoO2的放电平台和能量密度相同,但是其安全性以及热稳定性要远远优于LiCoO2,同样强于LiMn2O4和LiFePO4.较之LiFePO4,单斜晶系的Li3V2(PO4)3化合物拥有更高的Li+离子扩散系数以及更高的放电电压(3.6V、4.1V和4.6V)和能量密度(用碳包覆后为2 330 mWh/cm3).因此,对近十多年来单斜晶Li3V2(PO4)3的主要合成工艺,碳包覆及掺杂改性等方面的研究进行综述,并对单斜晶Li3V2(PO4)3正极材料的晶体结构、充放电机理、性能特点分别进行了介绍.     

阴离子氧化还原反应对富锂层状材料性能影响研究进展

富锂层状材料((1-x)LiMO2?xLi2MnO3)具有高的放电比容量和工作电压,低的成本,有希望成为下一代商业化的锂离子电池正极材料,但电压和容量衰减快、倍率性能差和氧气释放阻碍了其应用.针对该材料晶体结构和充放电机制的复杂性,从分子轨道理论的角度进行了阐述.概括了富锂层状材料改性研究工作(如离子掺杂、氧空位的形成...     

锂铌氧化物包覆改性Li[Li_(0.2)Co_(0.13)Ni_(0.13)Mn_(0.54)]O_2的研究

采用高离子导电率、电化学惰性的锂铌氧化物对富锂层状材料Li[Li0.2Co0.13Ni0.13Mn0.54]O2进行包覆改性研究.Li[Li0.2Co0.13Ni0.13Mn0.54]O2通过共沉淀-高温固相法合成,不同包覆量的复合材料通过一个简单的化学水解沉积的方法得到.研究了包覆材料的结构随温度变化对其主体材料结构、形貌及电化学性能的影响.XRD测试表明,包覆材料结构从LiNbO3(500℃)、LiNbO3-Li3NbO4(600~700℃)的混合相,到Li3NbO4(800℃)发生递变.包覆材料的电化学循环性能得到提升,混合相存在时尤为显著.     

正极材料Li[Ni_(1/3)Li_(1/9)Mn_(5/9)]O_2的结构和充放电过程研究

应用X射线衍射,选区电子衍射和同步X射线衍射等方法,对锂离子电池正极材料Li[Ni1/3Li1/9Mn5/9]O2的结构和充放电行为进行了研究.结果表明Li[Ni1/3Li1/9Mn5/9]O2可标定为单相α-NaFeO2,并具有3ahex.×3ahex.×3chex.超结构特征.电池充电时,伴随锂离子的脱出,相邻氧原子层间的静电斥力逐渐增大,当电压为3.8V时应力达到最大.接近4.6V时,晶胞常数c急剧下降,绝大多数Li 从材料的锂层拔出,Ni2 发生氧化.4.6～4.8V之间c增大,a变化很小,说明过渡金属层中的Li 拔出,而过渡金属离子的氧化状态未改变.     

EDTA络合制备锂离子电池正极材料Li1-xKxCoO2

采用EDTA络合溶胶-凝胶法制备出锂离子电池正极材料Li1-xKxCoO2,对Li1-xKxCoO2的成胶条件和形成过程进行探讨,并分别用XRD、SEM等手段对晶体结构、形貌等进行了研究.结果表明合成的Li1-xKxCoO2,粉体结晶良好,层状结构发育完善.在焙烧温度不高于700℃时就能够形成单一相的Li0.98K0.02CoO2,充放电实验表明,700℃,12h得到的材料具有最好的电化学性能.     

锂离子电池正极材料Li［CoxLi 1/3-x/3Mn2/3-2x/3］O2的制备与表征

采用柠檬酸盐法合成了Li［Co_xLi _{1/3-x/3}Mn_2/3-2x/3］O₂（x=0.1,0.2,0.3,0.4,0.5）正极材料. 利用X射线衍射(XRD), Raman光谱和红外光谱(FTIR)等方法研究不同质量分数的Co对材料晶体结构的影响, 并分析了原因. 对不同组分的材料进行了电化学性能测试, 结果表明, 当x=0.5时, 样品充放电容量高, 循环性能优良.      

多边形结构富锂锰基正极材料的可控制备及性能

本文通过水热合成法成功制备了一种富锂Li1.166(Mn0.6Ni0.2Co0.2)0.834O2正极材料。并通过X射线衍射（XRD）、扫描电子显微镜（SEM）和高精度电池测试系统分别对电极材料的结构、形貌和电化学性能进行了相应的表征和测试分析.结果表明,样品Li1.166(Mn0.6Ni0.2Co0.2)0.834O2具有较好的多面体结构特点以及优异的电化学性能,该电极材料相对于商用LiCoO2材料（约135mAh g?1）具有更高的充放电比容量,其值分别为363.8 mAh g?1 和 222.2 mAh g?1,首次库仑效率为61.1%.循环100周之后可逆放电比容量仍然可以达到235.5 mAh g?1.该富锂Li1.166(Mn0.6Ni0.2Co0.2)0.834O2正极材料在高能量密度动力电池发展中具有良好的应用前景和广阔的市场空间.     

Investigation on the electrochemical activation process of Li1.20Ni 0.32Co0.004Mn0.476O2

The lithium-rich layered oxides are one of the most attractive cathode materials for lithium-ion batteries.Here,two types of Li1.20Ni0.32Co0.004Mn0.476O2 were synthesized using Li2CO3 and LiOH as lithium sources.An electrochemical activation process occurs in Li1.2Ni0.32Co0.004Mn0.476O2 prepared from Li2CO3(LLO-1),while no obvious activation in Li1.2Ni0.32Co0.004Mn0.476O2 prepared from LiOH(LLO-2) is observed.Via advanced scanning transmission electron microscopy(STEM),we found that Li2MnO3-like structure is rich in the surface region of LLO-2.The study provides a direct explanation for the electrochemical activation of lithium-rich materials.The sample with more LiMO2-like phase at the surface region shows a better cycling performance.It is likely that more LiMO2-like phase at the surface region could stabilize the interface and improve the cycling performance of the Li-rich cathode materials.     

锂插入TiS_2的阴极反应过程及其相应的结构变化研究

本文从 ＴｉＳ２和 ＬｉｘＴｉＳ２的电子衍射花样和 Ｘ－射线衍射谱分析得出 Ｌｉ＋插入ＴｉＳ２的阴极反应过程。 Ｌｉ＋先插入 ＴｉＳ２，而后有序化形成 ＬｉＴｉＳ２相。由 Ｘ－射线衍射数据分析得出，新相 ＬｉＴｉＳ２的重复周期 Ｉｃ＝１８．４０Ａ。电子衍射花样表明过量 Ｔｉ形成了超点阵，Ｔｉ在点阵中形成钉扎。伏安循环曲线表明过量Ｔｉ阻止Ｌｉ的插入和移出 ＴｉＳ２本文否定了 Ｌｉ＋插入 ＴｉＳ２只形成一级的 ＬｉｘＴｉＳ２的结论。     

Tuning Li3PO4 modification on the electrochemical performance of nickel-rich LiNi0.6Co0.2Mn0.2O2

Surface deterioration occurs more easily in nickel-rich cathode materials with the increase of nickel content. To simultaneously pre-vent deterioration of active cathode materials and improve the electrochemical performance of the nickel-rich cathode material, the surface of nickel-rich LiNi0.6Co0.2Mn0.2O2 cathode material is decorated with the stable structure and conductive Li3PO4 by a facile method. The LiNi0.6Co0.2Mn0.2O2–1wt％, 2wt％, 3wt％Li 3PO4 samples deliver a high-capacity retention of more than 85％ after 100 cycles at 1 C under a high voltage of 4.5 V. The effect of different coating amounts (0–5wt％) for the LiNi0.6Co0.2Mn0.2O2 cathode is analyzed in detail. Results show that 2wt％ coating of Li3PO4 gives better performance compared to other coating concentrations. Detailed analysis of the structure of the samples during the charge?discharge process is performed by in-situ X-ray diffraction. It is indicated that the modification for LiNi0.6Co0.2Mn0.2O2 cathode could protect the well-layered structure under high voltages. In consequence, the electrochemical performance of modified samples is greatly improved.     

Coupling effect of the conductivities of Li ions and electrons by introducing LLTO@C fibers in the LiNi0.8Co0.15Al0.05O2 cathode

To probe the coupling effect of the electron and Li ion conductivities in Ni-rich layered materials(LiNi0.8Co0.15Al0.05O2,NCA),lithium lanthanum titanate(LLTO)nanofiber and carbon-coated LLTO fiber(LLTO@C)materials were introduced to polyvinylidene difluoride in a cathode.The enhancement of the conductivity was indicated by the suppressed impedance and polarization.At 1 and 5 C,the cathodes with coupling conductive paths had a more stable cycling performance.The coupling mechanism was analyzed based on the chemical state and structure evolution of NCA after cycling for 200 cycles at 5 C.In the pristine cathode,the propagation of lattice damaged regions,which consist of high-density edge-dislocation walls,destroyed the bulk integrity of NCA.In addition,the formation of a rock-salt phase on the surface of NCA caused a capacity loss.In contrast,in the LLTO@C modified cathode,although the formation of dislocation-driven atomic lattice broken regions and cation mixing occurred,they were limited to a scale of several atoms,which retarded the generation of the rock-salt phase and resulted in a pre-eminent capacity retention.Only NiO phase“pitting”occurred.A mechanism based on the synergistic transport of Li ions and electrons was proposed.     

WO3和V2O5薄膜电致变色器件特性研究

采用电子束和热蒸发分别制备了WO3和V2O5薄膜,研究了WO3薄膜的电化学、循环耐用性、电致变色特性,分析了V2O5薄膜的Li离子储存性能、Li离子的注入／退出可逆性以及离子注入对光学性能的影响,并讨论了WO3薄膜/Li离子电解质／V2O5薄膜构成的灵巧窗器件的电致变色特性．实验结果表明,这样构成的灵巧窗器件具有比较理想的光学调制性能．     

Application prospects of high-voltage cathode materials in all-solid-state lithium-ion batteries

All-solid-state lithium-ion batteries are lithiumion batteries with solid-state electrolytes instead of liquid electrolytes.They are hopeful in solving the safety problems of lithium-ion batteries,once their large capacity and long life are achieved,they will have broad application prospects in the field of electric vehicles and large-scale energy storage.The working potential window of solid electrolytes is wider than that of liquid electrolytes,so high-voltage cathode materials could be used in all-solidstate lithium-ion batteries to get higher energy density and larger capacity by elevating the working voltage of the batteries.The spinel LiNi0.5Mn1.5O4material,layered Li–Ni–Co–Mn–O cathode materials and lithium-rich cathode materials can be expected to be applied to all-solid-state lithium-ion batteries as cathode materials due to their highvoltage platforms.In this review,the electrochemical properties and structures of spinel LiNi0.5Mn1.5O4material,layered Li–Ni–Co–Mn–O cathode materials and lithiumrich cathode materials are introduced.More attentions are paid on recent research progress of conductivity and interface stability of these materials,in order to improve their compatibility with solid electrolytes as cathode materials in all-solid-state lithium-ion batteries and fully improve the properties of all-solid-state batteries.Finally,the existing problems of their application in all-solid-state lithium-ion batteries are summarized,the main research directions are put forward and their application prospects in all-solid-state lithium-ion batteries are discussed.