SnO2基锂离子电池负极材料研究进展

 作为一种N型半导体,二氧化锡基负极材料由于其拥有较高的理论比容量（782 mA·h·g^-1）、高能量密度等优势受到了广泛关注。然而,由于二氧化锡负极材料在充放电过程中的体积效应和本身导电性较差等导致的其循环性能和倍率性能较差,从而制约了其作为锂离子电池负极材料的应用。本文从二氧化锡的纳米化及复合化（包括其与金属氧化物、无定型碳、碳纳米管和石墨烯等复合）2 方面综述了二氧化锡基锂离子电池负极材料的研究进展,同时对SnO₂基锂离子电池负极材料的发展方向进行了展望。     

镍掺杂SnO2纳米微球锂离子电池负极材料的制备及其性能

利用简单的一步水热法制备高性能的镍掺杂SnO₂ 纳米微球锂离子电池负极材料. 利用扫描电镜(scanning electron microscope, SEM)、高分辨率透射电镜(high resolution transmission electron microscope, HRTEM)、拉曼分析仪、X射线衍射(X-ray diffraction, XRD)仪以及电化学性能测试仪器(如蓝电测试系统、电化学工作站)分别研究了镍掺杂对SnO₂ 微观形貌、组成、结晶行为及电化学性能的影响, 并得到了最佳反应时间. 实验结果表明：与纯SnO₂相比, 镍掺杂SnO₂ 纳米微球表现出了更好的倍率性能和优异的循环性能. 特别地, 反应时间为12 h 的5 % 镍掺杂SnO₂ 在100 mA/g 电流密度下的首次放电比容量为1 970.3 mA·h/g,远高于SnO₂ 的理论容量782 mA·h/g. 这是因为镍掺杂可适应庞大的体积膨胀, 避免了纳米粒子的团聚, 因此其电化学性能得到了显著改善.     

酚醛树脂热解炭的制备及其电化学行为的研究

采用SEM,XRD,恒流充放电等方法研究了一种新型开环自聚酚醛树脂在不同温度下炭化产物的形态、结构及电化学储锂行为。结果表明：酚醛树脂热解炭的微观形态为片层结构,具有较大的d002值,较小的Lc值和较大的La值;它的电化学性质呈现出含氢炭材料的行为,表现出高的储锂容量和较大的不可逆容量损失,随着炭化温度的提高,所得炭的储锂容量由600 ℃时的616mAh/g减小为800 ℃时的208 mAh/g,相应的不可逆容量损失也由600 ℃的219 mAh/g减小为800 ℃的31 mAh/g;探讨了该聚合物炭的储锂机制,认为除了锂对微晶石墨片层的插层作用之外,还可能存在锂离子与炭材料中氢原子的结合,导致放电电压的滞后。但随着热处理温度的提高,氢含量减少,上述电压滞后现象也随之减弱,直至消失。     

Sn/C复合材料的制备及作为锂离子电池负极材料的性能

采用SnCl2.2H2O乙醇溶液浸渍竹炭和NaBH4还原方法制备出一种锂二次电池负极用Sn/C复合材料。考察了复合材料中Sn含量对产物收率、微观结构及电化学性能的影响。结果表明,Sn2+大部分进入到竹炭的孔道中,并被还原为单质Sn;当单质Sn与复合材料质量比为42.5∶100时,复合电极材料具有555.1mAh/g的可逆容量,循环20次后容量保持在423.8 mAh/g,显示出较好的实用性能。     

Preparation and performance of novel LLTO thin film electrolytes for thin film lithium batteries

We prepared a series of lithium lanthanum titanate(LLTO) thin film electrolytes by radio frequency(RF) magnetron sputtering using LLTO targets in a N2 atmosphere.We also deposited the LLTO thin films in an Ar atmosphere under a same condition as references for comparison.The microstructure morphology and the composition of the thin films were investigated by X-ray diffraction(XRD),scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS),respectively.Results show that the thin film has an amorphous structure with a uniform surface and it is free of pinholes and cracks.Impedance measurements reveal that the ionic conductivity of the electrolytes is beneficial for all solid lithium batteries dependent on the lithium content at room temperature.We found that the amorphous LLTO thin film performs well and it has potential application in microbatteries for use in microelectronic devices.     

锂离子电池电极材料的研究进展

综述了国内近年来锂离子电池的正极和负极材料的研究进展，对正极材料中LICoO2，LiNiO2和LiMnO4，负极材料中的碳素和非碳素材料以及合金等的研究现状及发展趋势分别作了评述.。     

射频溅射ZrO_2薄膜的摩擦学特性

利用磁控射频反应溅射方法制备了 ＺｒＯ２薄膜。分析了工艺对薄膜结构的影响，结构与摩擦学特征的关系。研究表明，氧分压和基片温度是影响薄膜结构，从而影响其摩擦学特性的关键因素。     

水解法制备SnO_2纳米材料及作为锂离子电池负极的性能研究

分别使用十二烷基苯磺酸钠(SDBS)作为表面活性剂以及十二烷基苯磺酸钠(SDBS)和聚乙烯吡咯烷酮(PVP)作为双表面活性剂,采用水解法制备出SnO_2纳米材料,并研究了SnO_2纳米材料的形貌和作为锂离子电池负极时的电化学性能之间的关系.结果表明,所制备的SnO_2纳米颗粒均为球形,大小为45~75 nm,在双表面活性剂的调控下所制备的SnO_2纳米材料体积较大.所制备的SnO_2纳米颗粒均为具有金红石结构的锡石型,属于四方晶系.恒电流充放电循环测试结果表明,SnO_2纳米颗粒具有较高的放电比容量,首次放电比容量大约为1400~1600 m Ah/g,但是循环稳定性较差,循环5次以后样品的放电比容量衰减至400~700 m Ah/g.总之,双表面活性剂调控下,7h煅烧制备得到的SnO_2纳米材料相对较好,具有相对较大的比容量和相对较小的阻抗.     

ZnO薄膜的射频磁控溅射法制备及特性

利用射频磁控溅射镀膜工艺,在石英玻璃衬底上成功制备了ZnO薄膜．采用原子力显微镜、X射线衍射、拉曼光谱、荧光分光光度计及椭偏等检测手段对其特性进行了测试、分析．研究结果表明：该薄膜具有良好的C轴取向结晶度;最佳激发波长为265．00nnl,光致发光峰分别位于362．00、421．06和486．06nm;437cm^-1是ZnO晶体的特征拉曼峰,该峰的出现与最强的X射线衍射(002)峰相对应;薄膜折射率为2．01．     

CIGS薄膜材料研究进展

CIGS薄膜太阳电池具有低成本、高效率、性能稳定等优点,是最有发展前途的太阳能电池之一,受到了广泛关注．阐述了CI（G）S材料特性,分别介绍了多种制备方法,其中着重介绍共蒸发三步法这一制备小面积高效率电池的通用方法和在产业化生产中更理想的溅射后硒化法．     

特种石墨尾料用作锂离子电池负极的研究

特种石墨尾料具有低灰分、较高的石墨化度和较大的碳微晶尺寸等特点,有望用于锂离子电池的负极材料。通过XRD、SEM和比表面分析仪对特种石墨尾料石墨化处理前后样品的微观结构进行了分析对比,评价了其电化学性能,探讨了特种石墨尾料用于锂离子电池负极材料的可行性及对其进行石墨化处理的必要性。结果表明,特种石墨尾料可以直接用作低端负极材料的生产原料;经过高温石墨化处理后,负极材料的循环性能、首次库仑效率和可逆容量均得到不同程度提升,应用范围进一步扩大。     

Sb$_{\mathbf 2}$O$_{\mathbf 3}$/Sb 锂离子电池负极材料的制备及电化学性能

以多孔锑 (Sb) 为原料利用微氧化法制备了三氧化二锑/锑 (Sb$_{2}$O$_{3}$/Sb) 复合材料. 首先通过梯度试验确定微氧化温度, 接着通过控制微氧化时长来控制产物中 Sb$_{2}$O$_{3}$ 的含量. 在制备的 Sb$_{2}$O$_{3}$/Sb 复合材料中, Sb 能改善复合物的电子传输能力从而提升倍率性能. Sb$_{2}$O$_{3}$ 提供高容量, 且基于转化反应生成的 Li$_{2}$O 能阻止锑金属的团聚, 提高复合物的循环稳定性. 由于这种协同效应, Sb$_{2}$O$_{3}$/Sb 复合材料在电流密度为 200 mA$\cdot$g$^{-1}$ 时的首次库仑效率为 78.2%, 经过 100 圈循环后容量高达 729.6 mAh$\cdot$g$^{-1}$, 而当电流密度为 10 000 mA$\cdot$g$^{-1}$ 时, 容量仍保持为 203 mAh$\cdot$g$^{-1}$. 对比多孔锑, Sb$_{2}$O$_{3}$/Sb 复合材料的循环和倍率性能均有显著提高.     

Preparation and optical properties of composite thin films with embedded InP nanoparticles

InP nanoparticles embedded in SiO₂ thin films were prepared by radio-frequency magnetron co-sputtering. We analyzed the structure and growth behavior of the composite films under different preparation conditions. X-ray diffraction and Raman spectroscopy analyses indicate that InP nanoparticles have a polycrystalline structure. The average size of InP nanoparticles is in the range of 3–10 nm. The broadening and red shift of the Raman peaks were observed, which can be interpreted by the phonon confinement model. Optical transmission spectra indicate that the optical absorption edges of the films can be modulated in the visible light range. The marked blue shift of the absorption edge with respect to that of bulk InP is explained by the quantum confinement effect. The theoretical values of the blue shift predicted by the effective mass approximation model are different from the experimental results for the InP-SiO₂ system. Analyses indicate that the exciton effective mass of the InP nanoparticles is not constant and is inverse relative to the particles radius, which may be the main reason that results in the discrepancy between the theoretical and the experimental result. We discussed the possible transition of the direct band gap to the indirect band gap for InP nanoparticles embedded in SiO₂ thin films.     

硅基SiC薄膜的制备及性能研究

文章采用电子束物理气相沉积法在单晶Si(100)基片上制备了单层SiC薄膜和Al2O3/SiC双层膜,然后在不同温度下经氩气保护退火。通过X射线衍射仪(XRD)、原子力显微镜(AFM)对所制备的薄膜进行了结构和表面形貌分析。研究表明:退火后SiC薄膜由非晶态转为晶态,随退火温度的升高,薄膜结晶更充分,薄膜表面平均粗糙度变小;双层膜与单层膜相比,其SiC衍射峰有所增强,薄膜表面更加平滑。     

掺银TiO2薄膜的制备及其光催化性能

采用Ｓｏｌ－ｇｅｌ法在玻璃板表面制得均匀的ＴｉＯ２薄膜,并利用光催化还原法镀银得到掺银ＴｉＯ２薄膜。用掺银的ＴｉＯ２薄膜和未掺银的ＴｉＯ２薄膜在高压汞灯和太阳光的照射下,对有机物苯酚水溶液进行催化光解研究。结果表明掺银ＴｉＯ２薄膜的光催化活性明显大于未掺银ＴｉＯ２薄膜,这是提高ＴｉＯ２光催化效率的可行方法。     

Progress on Sn-based thin-film anode materials for lithium-ion batteries

Thin-film lithium-ion batteries are the most competitive power sources for various kinds of micro-electro-mechanical systems and have been extensively researched.The present paper reviews the recent progress on Sn-based thin-film anode materials,with particular emphasis on the preparation and performances of pure Sn,Sn-based alloy,and Sn-based oxide thin films.From this survey,several conclusions can be drawn concerning the properties of Sn-based thin-film anodes.Pure Sn thin films deliver high reversible capacity but very poor cyclability due to the huge volume changes that accompany lithium insertion/extraction.The cycle performance of Sn-based intermetallic thin films can be enhanced at the expense of their capacities by alloying with inactive transition metals.In contrast to anodes in which Sn is alloyed with inactive transition metals,Sn-based nanocomposite films deliver high capacity with enhanced cycle performance through the incorporation of active elements.In comparison with pure Sn anodes,Sn-based oxide thin films show greatly enhanced cyclability due to the in situ formation of Sn nanodispersoids in an Li2O matrix,although there is quite a large initial irreversible capacity loss.For all of these anodes,substantial improvements have been achieved by micro-nanostructure tuning of the active materials.Based on the progress that has already been made on the relationship between the properties and microstructures of Sn-based thin-film anodes,it is believed that manipulating the multi-phase and multi-scale structures offers an important means of further improving the capacity and cyclability of Sn-based alloy thin-film anodes.     

Aromatic carbon coated tin composites as anode materials for lithium ion batteries

Aromatic carbon coated tin composites (A/Sn) have been prepared by thermal decomposition of the stannous 1,8-naphthalenedicarboxylate precursors, which is a reformative preparation method. Sugar carbon coated tin composites (S/Sn) also are prepared as a contrast with the A/Sn composites. The morphology and composition of the products were characterized by Scanning Electricity Microscopy (SEM) and X-Ray Diffraction (XRD). Their electrochemical performance as anode materials for lithium ion batteries were investigated; the results indicated that these materials exhibited good performance, and the cycle stability of A/Sn composites is especially superior to the S/Sn composites due to its special carbon resource.     

电沉积和硒化制备CuInSe2薄膜

以石墨为阳极、钛片为阴极,采用恒电流法制备Cu-In预制膜,然后硒化处理得到CuInSe2薄膜.分析了预制膜和CuInSe2薄膜的相组成及其影响因素.结果表明:采用不同的电沉积工艺,可以得到不同相组成的Cu-In预制膜.在保证Cu/In小于1的条件下,降低InCl3浓度和H3Cit/CuCl2浓度比,选择较高电流,可以获得具有CuIn相和Cu2In相的Cu-In预制膜.含有CuIn相和Cu2In相的Cu-In预制膜,经硒化得到的CuInSe2薄膜具有单一CuInSe2相组成,并且符合化学剂量比要求;而只含有CuIn相的预制膜硒化后除了有CuInSe2相外还出现了CuSe相.     

工作气压对溅射沉积铜铟镓硒薄膜形态和光学性能的影响

采用射频磁控溅射法,通过直接溅射铜铟镓硒四元合金靶在镀有Mo背电极的soda-lime玻璃衬底上获得铜铟镓硒(CIGS)薄膜.利用X线衍射(X-ray diffraction,XRD)、扫描电子显微镜(scanning electron microscope,SEM)和X线能量色散谱仪(energy dispersive X-ray spectroscopy,EDS)研究薄膜的结构、表面形貌和组织成分的变化,并通过紫外-可见分光光度计(ultraviolet and visible spectrophotometer,UV/VIS)获得薄膜的透过率光谱,研究不同工作气压对CIGS薄膜晶体结构、表面形貌和光学性能的影响.实验结果表明:在工作气压为0.8 Pa时制得的薄膜表面均匀致密,可见光范围内透光率接近于零,nCu/nIn+Ga=0.83,nGa/nIn+Ga=0.3,nSe/nCu+In+Ga=1,证明溅射所得CIGS吸收层薄膜的性能接近高效吸收层的要求.