MoO_3电致变色薄膜的XPS研究

近年来 ,随着人们提倡节能和使用洁净能源 ,无机电致变色材料在建筑物采光控制系统和反射率可调表面的应用研究 ,已成为材料领域的一个新热点 .WO3、 MoO3等过渡金属氧化物薄膜具有良好的电致变色效应 ,是人们研究的重点 .其中 MoO3的电致变色效果要好于 IrO2、 TiOx、 CoO及 NiOx等电致变色材料 [1],而且它在可见光区有比 WO3更柔和的色彩 ,使人眼更易于适应其颜色变化 .着色态的 MoO3称为钼青铜 ,其开路记忆也好于钨青铜 [2].故 MoO3电致变色薄膜是极有潜力用于实用化的电致变色器件 .MoO3薄膜常用的制备方法有真空蒸 发、化学气…     

Collapse transition in thin films of poly(methoxydiethylenglycol acrylate)

The thermal behavior of poly(methoxydiethylenglycol acrylate) (PMDEGA) is studied in thin hydrogel films on solid supports and is compared with the behavior in aqueous solution. The PMDEGA hydrogel film thickness is varied from 2 to 422?nm. Initially, these films are homogenous, as measured with optical microscopy, atomic force microscopy, X-ray reflectivity, and grazing-incidence small-angle X-ray scattering (GISAXS). However, they tend to de-wet when stored under ambient conditions. Along the surface normal, no long-ranged correlations between substrate and film surface are detected with GISAXS, due to the high mobility of the polymer at room temperature. The swelling of the hydrogel films as a function of the water vapor pressure and the temperature are probed for saturated water vapor pressures between 2,380 and 3,170?Pa. While the swelling capability is found to increase with water vapor pressure, swelling in dependence on the temperature revealed a collapse phase transition of a lower critical solution temperature type. The transition temperature decreases from 40.6?°C to 36.6?°C with increasing film thickness, but is independent of the thickness for very thin films below a thickness of 40?nm. The observed transition temperature range compares well with the cloud points observed in dilute (0.1?wt.%) and semi-dilute (5?wt.%) solution which decrease from 45?°C to 39?°C with increasing concentration.     

Dependence of electrochemical properties of vanadium oxide films on their nano- and microstructures

Platelet- and fibrillar-structured V2O5 films have been prepared by solution methods, and their electrochemical Li+ intercalation properties have been studied. Platelet film consists of 20-30 nm sized V2O5 particles with random orientation, whereas fibrillar film is comprised of randomly oriented fibers though most of them protrude from the substrate surface. These platelet- and fibrillar-structured films exhibit relatively larger surface area and shorter diffusion path for Li+ intercalation than plain thin film structure. The processing methods, the discharge capacity, and cyclic performance of these films are compared with those of the conventional plain structured film.     

Na-Mn-O正极材料的合成及电化学性能

以Mn(CH3COO)2·4H2O为锰源, 以Na2CO3为钠源, 通过溶液-凝胶法合成干凝胶前驱体, 将前驱体在空气气氛中焙烧得到Na-Mn-O正极材料. 并用傅立叶红外光谱(FT-IR), 热重分析(TG), X射线衍射(XRD), 扫描电镜(SEM), 恒流充放电测试等对材料结构和性能进行研究. 结果表明,600 ℃焙烧的样品为结构稳定的层状锰酸钠, 属于六方层状P2结构, 空间群为P63/mmc, 通过PowderX软件计算得到其晶胞参数为a=0.284 nm, c=1.116 nm. Na-Mn-O正极材料在Li+嵌入和脱出过程中, 部分Na+从层状主晶格中脱出, 使得Li+在MnO6层间的嵌/脱阻力减小(由于Na+(0.095 nm)半径比Li+(0.076 nm)大), 电化学性能明显改善. 在充放电电流密度为25 mA·g-1, 电压在2.0-4.3 V范围时, 600 ℃焙烧的样品第二次放电容量高达176 mAh·g-1, 20次循环后, 容量保持率仍有90.9%.     

Silver nanoparticle monolayer-to-bilayer transition at the air/water interface as studied by the GISAXS technique: application of a new paracrystal model

An original diffraction model for the analysis of grazing-incidence small-angle X-ray scattering (GISAXS) from the nanoparticle Langmuir films was developed. This model relies on the concept of the 2D hexagonal paracrystal and employs the distorted-wave Born approximation that is relevant for GISAXS measurements at the air/water interface when the angle of incidence is close to the critical value. The model comprises the cases of the close-packed nanoparticle monolayer and bilayer with the AB-type layer stacking. In this way, both the lateral (along the interface) and vertical (normal to the interface) correlations of the nanoparticle positions can be analyzed. The model was applied to an in situ GISAXS study of the formation of a silver nanoparticle Langmuir film during compression at the air/water interface in the Langmuir-Blodgett trough. Spherical nanoparticles of 5.8 ± 0.6 nm diameter were employed. Different compression stages starting from the submonolayer up to the monolayer collapse via bilayer formation were analyzed in terms of the mean lateral interparticle distance, degree of paracrystal disorder, interlayer distance, vertical disorder, and layer-stacking type in the bilayer as well as the ratio between the monolayer and bilayer coverage in the final film. The model developed is applicable to any nanoparticle Langmuir film formed at the air/liquid interface to extract structural parameters on the nanoscale. The particular results obtained have direct implications on the preparation of silver plasmonic templates with "hot spots" for surface-enhanced Raman scattering.     

Enhancement of intercalation properties of V2O5 film by TiO2 addition

Although it is well-known that TiO2 incorporation can greatly improve the cyclic stability of V2O5, the influences of TiO2 addition on the Li+ intercalation properties of V2O5 remain an issue of debate in literature. In this paper, we report on a systematic investigation of the preparation and intercalation properties of V2O5-TiO2 mixture films. The present work demonstrates that high Li+ intercalation rates and capacity in V2O5 films are achievable with TiO2 addition. For example, the addition of 20 mol % Ti into V2O5 polycrystalline demonstrated an approximated 100% improvement in Li+ intercalation performance as compared to single V2O5 electrodes. Such enhancement in intercalation properties of V2O5 films with TiO2 addition was attributed to changes in microstructure, crystallinity, and also a possible lattice structure and interaction force between adjacent layers in V2O5.     

In situ spectroelectrochemical behaviour of nanocrystalline TiO_2 thin films electrode fabricated by pulsed laser deposition

Nanocrystalline titanium oxide thin films have been successfully deposited on ITO coated glass by pulsed laser ablation of metallic Ti target in O_3/O_2 ambient gases. The intercalation of Li ions in the anatase TiO_2 film electrode is examined by cyclic vohammetry. The electrochromic behaviour of TiO_2 electrode is investigated by in-situ visible transmittance measurement, and two absorption bands at 420 and 650 nm are observed. The absorption falling and rising in color changing with excellent revisibility is relative to the insertion and deintercalation processes of Li ion. These resuits suggest that nanocrystalline titanium oxide films fabricated by pulsed laser deposition exhibit excellent spectroelectrochemical property.     

MoO3电致变色薄膜的XPS研究

Molybdenum oxide films were fabricated successfully by spin coating from Li＋ doped peroxo polymolybdate solution via sol gel technique.Their electrochemical and electrochromic properties were investigated by cyclic voltammetry and in situ UV transmittance measurements.The results showed that the films possessed excellent electrochemical stability and reversibility.The electrochromic mechanism of the MoO3 was discussed by using results obtained from X ray photoelectron spectroscopy (XPS).The results showed that the most part of the Mo6＋ in MoO3 film was reduced to Mo5＋ and Mo4＋ ions during the Li＋ intercalation process,Mo4＋ was oxidized to Mo5＋ and part of Mo5＋ was oxidized to Mo6＋ again during the Li＋ deintercalation process.So it was considered that Mo4＋ ions existed in the colored MoO3 films.     

新型固体电解质Ce5.2RE0.8MoO15-δ 的合成及电性质

采用溶胶-凝胶方法合成了系列新型氧化物Ce5.2RE0.8MoO15-δ(RE=Ce, Y, La, Sm, Gd, Dy, Ho, Er). 通过XRD, Raman和XPS等手段对氧化物的结构进行了表征, 采用交流阻抗谱测试其导电性能. 研究结果表明, RE3+的掺杂可增加氧离子的空位浓度, 改善母体电导率, 晶胞参数随RE3+半径的增大而增大. 掺杂离子Dy3+的半径(0.0908 nm) 与母体基质离子Ce4+的半径(0.0920 nm) 相近, 形成的掺杂氧化物晶格弹性应变最小, RE3+与氧空位间的缔合焓(ΔHA)最小, 因而氧化物Ce5.2Dy0.8MoO15-δ具有相对较高的电导率(7.02×10-3 S/cm)和较低的激活能(1.056 eV).     

退火温度对PLD法制备ZnO:Eu3+,Li+薄膜结构和发光性质的影响

采用脉冲激光沉积(PLD)法在Si(111)衬底上制备了Eu3+,Li+共掺杂的ZnO薄膜,分别在450,500,550和600℃条件下进行退火,退火气氛为真空。利用X射线衍射(XRD)仪和荧光分光光度计研究了退火温度对薄膜结构和光致发光(PL)的影响。研究结果表明,Eu3+,Li+共掺杂的ZnO薄膜具有c轴择优取向,Eu3+,Li+没有单独形成结晶的氧化物,均以离子形式掺入ZnO晶格中。PL谱中有较宽的ZnO基质缺陷发光,ZnO基质与稀土Eu3+之间存在能量传递,但没有有效的能量传递。随着退火温度的增加,薄膜发光先增强后减弱,退火温度为550℃时发光最强。当用395 nm的激发光激发样品时,仅观察到稀土Eu3+在594 nm附近的特征发光峰,但发光强度随退火温度变化不明显。     

Size‐Independent Fast Ion Intercalation in Two‐Dimensional Titania Nanosheets for Alkali‐Metal‐Ion Batteries

Compared to lithium ions, the fast redox intercalation of large‐radius sodium or potassium ions into a solid lattice in non‐aqueous electrolytes is an elusive goal. Herein, by regulating the interlayer structure of stacked titania sheets through weakened layer‐to‐layer interactions and a robustly pillared gallery space, the two‐dimensional channel between neighboring sheets was completely open to guest intercalation, allowing fast intercalation that was practically irrespective of the carrier‐ion sizes. Regardless of employing regular Li or large‐radius Na and K ions, the material manifested zero strain‐like behavior with no significant change in both host structure and interlayer space, enabling comparable capacities for all tested ions along with excellent rate behaviors and extraordinarily long lifetimes, even with 80‐μm‐thick electrodes. The result highlights the importance of interlayer structural features for unlocking the electrochemical activity of a layered material.     

Sr2MgSiO5∶Ce3+的发光性质研究

报道了Sr2MgSiO5∶Ce3+荧光粉的发光性质.     

Directed Self-assembly of Vertical PS-b-PMMA Nanodomains Grown on Multilayered Polyelectrolyte Films

Layer-by-layer polyelectrolyte self-assembly, a common method for preparing high-quality ultra-thin films, was employed to direct the self-assembly behavior of polystyrene-block-poly(methyl methacrylate)(PS-b-PMMA) block copolymer for the first time. Differing from the previous neutral polymer brushes anchored to silicon substrates via chemical modification, polyelectrolyte multilayers(PEMs) were anchored by electrostatic interaction and provided a stable, smooth, and neutral interface. In the present study, PS-b-PMMA was deposited on poly(acrylamide hydrochloride)/poly(acrylic acid)(PAH/PAA) PEMs prepared by layer-by-layer self-assembly to successfully yield vertical nanodomains after thermal annealing. Seven layered PEMs revealed an excellent, smooth surface, with a low roughness of 0.6 nm. The periodic structure with interlamellar spacing of 47 nm was determined by grazing-incidence small-angle X-ray scattering(GISAXS). The morphology of the PS-b-PMMA nanodomains depended on the polyanion-to-polycation concentration ratio, which is related to the interaction between the block copolymer and the substrate. Our results demonstrate that layer-by-layer self-assembly is a helpful method for the phase separation of block polymers and the fabrication of vertical, ordered nanodomains.     

锂-氧化铜电池反应机理(Ⅰ)——光电化学方法研究阴极嵌入反应

采用光电化学方法现场研究了锂-氧化铜电池的嵌入反应,氧化铜电极光电流的变化直观地反映了该电化学嵌入过程.发现锂离子嵌入氧化铜电极的反应始于2.5V(vs.Li/Li⁺),锂以施主杂质状态存在于氧化铜晶格中,改变了阴极的半导体性质.在较低电位下,可能有产生氧化亚铜的后续反应.     

In situ spectroelectrochemical behaviour of nanocrystalline TiO2 thin films electrode fabricated by pulsed laser deposition

Nanocrystalline titanium oxide thin films have been successfully deposited on IT0 coated glass by pulsed laser ablation of metallic Ti target in 0₃/0₂ ambient gases. The intercalation of Li ions in the anatase TiO₂ film electrode is examined by cyclic voltammetry. The electrochromic behaviour of TiO₂ electrode is investigated byin-situ visible transmittance measurement, and two absorption bands at 420 and 650 nm are observed. The absorption falling and rising in color changing with excellent revisibility is relative to the insertion and deintercalation processes of Li ion. These results suggest that nanocrystalline titanium oxide films fabricated by pulsed laser deposition exhibit excellent spectroelectrochemical property. Project supported by the National Natural Science Foundation of China (Grant No. 29783001) and State Key Laboratory for Physical Chemistry of Solid Surface of Xiamen University (1997).     

Self-assembly of PbTe quantum dots into nanocrystal superlattices and glassy films

Monodisperse lead telluride (PbTe) nanocrystals ranging from approximately 4 to 10 nm in diameter are synthesized to provide quantum dot building blocks for the design of novel materials for electronic applications. Two complementary synthetic approaches are developed that enable either (1) isolation of small quantities of nanocrystals of many different sizes or (2) the production of up to 10 g of a single nanocrystal size. PbTe nanocrystals are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and optical absorption. Assembly of PbTe nanocrystals is directed to prepare nanocrystal solids that display either short-range (glassy solids) or long-range (superlattices) packing order by varying deposition conditions. Film order and average interparticle spacing are analyzed with grazing-incidence small-angle X-ray scattering (GISAXS) and high-resolution scanning electron microscopy (HRSEM). We perform the first optical and electronic studies of PbTe solids and demonstrate that chemical activation of these films enhances conductivity by approximately 9-10 orders of magnitude while preserving their quantum dot nature.     

锂离子电池电极材料研究进展

本文综述了锂离子电池中正、负电极材料的制备、结构与电化学性能之间的关系。正极材料包括嵌锂的层状L ixMO 2 和尖晶石型L ixM 2O 4 结构的过渡金属氧化物(M =Co、N i、M n、V ) , 负极材料包括石墨、含氢碳、硬碳和金属氧化物。侧重于阐述控制锂离子电池循环过程中可逆嵌锂容量和稳定性的嵌锂电极材料的结构性质。给出118 篇参考文献。     

电泳沉积法制备V2O5薄膜的结构和性能

V2O5 thin films were successfully prepared on ITO substrate with electrophoresis deposition (EDP) through V2O5 sol. X-ray diffraction and scanning electron microscopy were used for studying the structure of the films. The optical and electrochemical properties were measured by the transmittance spectra and cyclic voltammetry measurements, respectively. It is found that V2O5 thin films deposited by EDP are a compact microstructure with finer adhesive force with ITO substrate and the thickness is uniform. During the cycle experiment, the films exhibited reversible two-color (yellow at oxidation and green at reduction) with a maximum transmittance change of around 30%. Moreover, the films had an excellent cycle for lithium intercalation/deintercalation and good cycle stability, the cycle efficiency for the 50th cycle was 88.02% and the films still had fine adhesive force with ITO substrate with no dissolving over more than 50 cycles. The Li+ diffusion coefficient in V2O5 thin film was 5.10×10-12 cm2/s by the electrochemical impedance spectra method. All results indicate that V2O5 thin films by the electrophoresis deposition may be suitable for the use in the electrochromic devices.     

Quantitative nanoorganized structural evolution for a high efficiency bulk heterojunction polymer solar cell

We have developed an improved small-angle X-ray scattering (SAXS) model and analysis methodology to quantitatively evaluate the nanostructures of a blend system. This method has been applied to resolve the various structures of self-organized poly(3-hexylthiophene)/C61-butyric acid methyl ester (P3HT/PCBM) thin active layer in a solar cell from the studies of both grazing-incidence small-angle X-ray scattering (GISAXS) and grazing-incidence X-ray diffraction (GIXRD). Tuning the various length scales of PCBM-related structures by a different annealing process can provide a flexible approach and better understanding to enhance the power conversion of the P3HT/PCBM solar cell. The quantitative structural characterization by this method includes (1) the mean size, volume fraction, and size distribution of aggregated PCBM clusters, (2) the specific interface area between PCBM and P3HT, (3) the local cluster agglomeration, and (4) the correlation length of the PCBM molecular network within the P3HT phase. The above terms are correlated well with the device performance. The various structural evolutions and transformations (growth and dissolution) between PCBM and P3HT with the variation of annealing history are demonstrated here. This work established a useful SAXS approach to present insight into the modeling of the morphology of P3HT/PCBM film. In situ GISAXS measurements were also conducted to provide informative details of thermal behavior and temporal evolution of PCBM-related structures during phase separation. The results of this investigation significantly extend the current knowledge of the relationship of bulk heterojunction morphology to device performance.     

锂嵌入对α-V2O5中O2p和V3d轨道电子结构的影响

运用第一性原理计算了锂嵌入对α-V2O5中O2p和V3d轨道电了结构的影响．计算结果表明，不同的锂嵌入位置对O2p和V3d轨道的电了结构有着不同的影响．但锂的嵌入会减弱了V2O5中V=O1键，同时导致V3d导带的劈裂变窄或消失和HO2p价带变宽．最后计算出从每个Li2s轨道到V3d轨道的电子传递数为0．52．