Densification and lithium ion conductivity of garnet-type Li7-xLa3Zr2-xTaxO12 （x=0.25） solid electrolytes

The garnet-type Li7La3Zr2O12 ceramic is a promising solid electrolyte for all-solid-state secondary lithium batteries. However, it faces the problem of lithium volatilization during sintering, which may cause low density and deterioration of ionic conductivity. In this work, the effects of sintering temperature and addition on the density as well as the lithium ion conductivity of Li7-xLa3Zr2-xTaxO12 (LLZTO, x=0.25) ceramics prepared by solid state reaction have been studied. It is found that optimization of the sintering temperature leads to a minor increase in the ceramic density, yielding an optimum ionic conductivity of 2.9×10-4 S·cm-1 at 25℃. Introduction of Li 3 PO 4 addition in an appropriate concentration can obviously increase the density, leading to an optimum ionic conductivity of 7.2×10-4 S·cm-1 at 25℃. This value is superior to the conductivity data in most recent reports on the LLZTO ceramics.     

纳米石榴石固体电解质粉体在聚合物电解质中的均匀分散

固态锂电池(SSLBs)因采用金属锂负极和固体电解质,具有提高能量密度和安全性的潜质。固体电解质作为固态锂电池的关键材料,对电池性能有重要影响。其中,聚合物-石榴石型复合固态电解质因结合了聚合物电解质的易加工性以及石榴石电解质的热稳定性和高离子电导率的优点,在固态电池规模化制造中具有良好的应用前景。然而,由于纳米固体电解质粉体的表面能高、与有机物的界面兼容性差,导致纳米锂镧锆氧颗粒在聚合物基体中容易发生团聚,进而导致复合电解质的离子电导率降低。本工作引入硅烷偶联剂3-缩水甘油氧基丙基三甲氧基硅烷(GPTMS)对Li_6.4La₃Zr_1.4Ta_0.6O₁₂(LLZTO)的表面进行改性,旨在改善LLZTO颗粒在溶剂和聚合物基体中的分散性。LLZTO纳米颗粒表面的羟基与GPTMS分子反应形成共价键,在颗粒表面形成一层厚度约5 nm的GPTMS修饰层。GPTMS中具有亲脂性的环氧基团,使改性后的LLZTO纳米颗粒(LLZTO@GPTMS)在有机溶剂中均匀分散。粒度分布实验表明,LLZTO...     

Evolutions of Crystal Structure, Stoichiometry and Electrochemical Behavior with Co Substitution in LiNi1-yCoyO2 Positive Electrodes

LiNi1-yCoyO2（0.1 ≤ y ≤ 0.4） positive electrode materials are synthesized by a chemical method with stoichiometric acetates of related cations. Their crystal structure, stoichiometry and electrochemical behaviors versus Co concentration are investigated by x-ray diffraction, synchrotron-based x-ray absorption fine structure and galvanostatic cycling ts. The results reveal that the non-stoiehiometric Ni^2＋, Li/Ni cation mixing and polarization are reduced as the amount of Co substitution increases, clearly indicating that the Co element is a medium for easily oxidizing Ni^2＋ to Ni^3＋ during the synthesis process.     

离子导体载流子输运与存储的界面调控

离子导电材料既可以是载流子主要为离子的纯离子导体,也可以是载流子同时包括离子和电子的混合离子导体.这两类材料是电化学能量转换与储存、化学传感以及选择性透过膜等器件的关键材料.在这些器件中,均存在电极与电解质、颗粒与颗粒、不同晶粒之间的二维或三维的异质结界面.因此,离子与电子在异质结中的输运性质对器件性能有重要的影响.但...     

Correlation between lithium storage and diffusion properties and electrochromic characteristics of WO3 thin films

As essential electrochromic(EC) materials are related to energy savings in fenestration technology,tungsten oxide(WO3) films have been intensively studied recently.In order to achieve better understanding of the mechanism of EC properties,and thus facilitate optimization of device performance,clarification of the correlation between cation storage and transfer properties and the coloration performance is needed.In this study,transparent polycrystalline and amorphous WO3 thin films were deposited on SnO2:F-coated glass substrates by the pulsed laser deposition technique.Investigation into optical transmittance in a wavelength range of 400-800 nm measured at a current density of 130 μA·cm-2 with the applied potential ranging from 3.2 to 2.2 V indicates that polycrystalline films have a larger optical modulation of ～ 30% at 600 nm and a larger coloration switch time of 95 s in the whole wavelength range compared with amorphous films(～ 24% and 50 s).Meanwhile,under the same conditions,polycrystalline films show a larger lithium storage capacity corresponding to a Li/W ratio of 0.5,a smaller lithium diffusion coefficient(2×10-12cm2·s-1 for Li/W=0.24) compared with the amorphous ones,which have a Li/W ratio of 0.29 and a coefficient of ～2.5×10-11cm2·s-1 as Li/W=0.24.These results demonstrate that the large optical modulation relates to the large lithium storage capacity,and the fast coloration transition is associated with fast lithium diffusion.     

异常大磁阻La-Sn-Mn-O外延单晶薄膜的研究 *

首次报道采用脉冲激光沉积方法在(100)LaAlO₃ 单晶基底上外延生长La-Sn-Mn-O薄膜 ,由X射线的衍射分析确定薄膜属于钙钛矿型结构 .薄膜在低温发生金属到半导体转变 ,它的电阻随磁场的变化而变化 ,其磁阻的最大变化率约为 1 0 3 ,表明此薄膜具有异常大磁阻效应 .磁化强度的测量表明其室温为顺磁性低温为铁磁性 .居里温度值与薄膜出现最大磁阻变化率的温度值十分接近 ,表明其中的磁阻效应是与铁磁到顺磁转变紧密相连的 .为进一步探讨La-Sn-Mn-O在将来集成薄膜器件中的应用前景 ,测量了薄膜表面的平整度 .