线切割多晶硅硅泥制备锂离子电池负极材料

硅基材料作为锂离子电池负极的理论容量达到4 200 mAh·g~(-1),被认为是最有发展前景的负极材料。但其体积膨胀过大,导致循环稳定性较差。通过球磨+碳包覆的方法,对线切割的纳米片层状多晶硅硅泥进行改性,使其作为锂离子电池负极材料的电化学性能得到了改善。结果表明,球磨使原料硅泥粒径明显减小。在电流密度为200 mA·g~(-1)时,原料硅泥球磨20 h后碳包覆的C-Si_(20)的首次充电比容量为1 784.2 mAh·g~(-1)。循环75次后充电比容量为640 mAh·g~(-1),充放电库伦效率保持在98%以上。材料具有比较好的循环性能,可以为光伏产业硅泥废料的回收再利用提供一定的借鉴意义。     

多孔硅/硅钛合金的制备及在锂离子电池负极上的应用

以钛掺杂介孔二氧化硅SBA-15为前驱体,用镁热还原法制备多孔硅/硅钛合金复合材料。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和红外光谱(FT-IR)等方法对复合材料进行表征;利用恒电流充放电对复合材料作为锂离子电池负极材料的电化学性能进行分析。结果表明,多孔结构为体积膨胀提供了缓冲空间,硅钛合金的存在起到支撑骨架的作用,同时一定程度上改善了负极材料的导电性,多孔硅/硅钛合金复合材料具有较好的循环稳定性,0.1C循环50圈后可逆容量为801mAh/g,倍率性能也较单质硅材料大大提高,1C倍率下放电容量为618.9mAh/g。     

具有石墨碳骨架结构的硅碳负极材料的制备与电化学性能研究

硅碳材料作为锂离子电池负极材料具有广阔地发展前景。利用水热法和高温碳化法制备了蔗糖碳/硅复合材料(SC/Si),并在此基础上与石墨复合制备出具有石墨导电骨架结构的蔗糖碳/硅-石墨复合材料(SC/Si-Gr),并探究其作为锂离子电池负极材料电化学和电池性能。结果表明，蔗糖碳均匀包覆在纳米硅表面，形成的蔗糖碳/硅复合材料的电化学性能和电池性能随着蔗糖碳含量增加而提高。随着石墨的引入，构建的SC/Si-Gr三元复合材料的电化学性能得到进一步提升。当蔗糖：硅：石墨投料质量比为1∶1∶0.5时，形成的SC/Si-Gr(1∶1∶0.5)复合材料，在电流密度为0.1 A/g条件下，第三圈稳定之后的放电比容量为1 005.1 mAh/g;循环100圈之后放电比容量为819 mAh/g,充放电库伦效率保持在98%左右。在1 A/g大电流密度下，平均放电比容量为437.91 mAh/g。这归功于石墨的加入形成有效的导电骨架结构，提高了首次循环库伦效率，加速锂离子的传输速率，使蔗糖碳/硅-石墨复合材料呈现出良好的循环稳定性和充放电倍率性能。     

Cu2+掺杂高密度LiFePO4/C正极材料的合成及性能

以高密度FePO4作为前躯体,Cu(Ac)2为掺杂源,通过高温固相法合成了高振实密度的锂离子电池正极材料LiFe1-xCuxPO4/C(x=0、0.01、0.015、0.02、0.025).采用X粉末衍射(XRD)、电子扫描显微镜(SEM)、循环伏安法(C-V)和恒电流充放电对合成的材料掺杂进行了结构、形貌和电性能表征和分析研究.结果表明, 所合成的掺杂复合材料LiFe1-xCuxPO4/C为典型的橄榄石型结构,结晶度高,具有较高的振实密度.掺杂Cu2+离子在很大程度上可以提高LiFePO4的电化学性能,当Cu含量为2.0%(质量分数)时,LiFe0.98Cu0.02PO4/C的振实密度可以达到1.98g/cm3,比容量为最大值,0.1C倍率放电可达150.0mAh/g,体积比容量为297.0mAh/cm3;2C倍率放电比容量仍可以达到127.3mAh/g以上,体积比容量为252.1mAh/cm3.     

掺杂对LiFePO_4电化学性能的影响

用水热法制备LiFe_(0.95)M_(0.05)PO_4(M=Mg,Ni,Co),研究了掺杂对材料电化学性能的影响.结果表明,液相Fe位掺杂合成的LiFe_(0.95)M_(0.05)PO_4具有纯相橄榄石结构、结晶良好、粒径均匀;Fe位掺杂可增强材料的可逆性和导电性,提高其1C倍率下的电化学容量和循环稳定性;LiFe_(0.95)Mg_(0.05)PO_4,LiFe_(0.95)Ni_(0.05)PO_4和LiFe_(0.95)Co_(0.05)PO_4三种材料的1C倍率首次放电比容量分别为133.1 mAh·g~(-1),128.4 mAh·g~(-1)和135.2 mAh·g~(-1);三种掺杂离子中Co~(2+)掺杂的效果最好,0.1C和1C倍率放电循环30次后的容量衰减率仅为5.7%和9.5%.     

大倍率二氧化硅/碳复合材料的制备及电化学性能表征

为了满足新能源储能及电动汽车对锂离子电池持续快速充电、慢速放电性能的要求,以正硅酸乙酯为二氧化硅前驱体,在两亲性炭材料(ACM)与聚乙二醇400(PEG400)形成的氢键限域体系中制备了大倍率二氧化硅/碳复合锂电负极材料(SiO_2-130/C)。材料表征结果表明,二氧化硅的粒径由500nm(未限域)降低到130nm(限域),同时,富碳的ACM在二氧化硅纳米颗粒表面构建了导电性良好的碳框架。在0.1A·g~(-1)和1A·g~(-1)的电流密度下,SiO_2-130/C的可逆比容量分别为527mAh·g~(-1)和347mAh·g~(-1),且在1A·g~(-1)的电流密度下连续400个充放电循环后,仍具有483 mAh·g~(-1)的可逆比容量,表现出优异的倍率性能及稳定的电化学性能。     

LiFe_(1-x)Ni_xPO_4复合正极材料的制备及性能研究

采用两步固相原位烧结掺杂法制备了一系列镍掺杂的锂离子电池正极材料LiFe1-xNixPO4(x=0、0.03、0.05、0.07、0.10、0.15).Ni替代部分Fe,改变了LiFePO4的晶胞参教,细化了晶粒.充放电实验研究表明,低放电倍率(0.1C)时,LiFe0.095Ni0.05PO4的首次放电容量最大,为155mAh/g,较LiFePO4增加了22.8%;0.5C时,其容量为132mAh/g,较LiFePO4增加了14.7%;放电倍率增加为1C时,其容量也能达到122mAh/g,较LiFePO4增加了16.1%.适量掺杂Ni可提高LiFePO4的充放电比容量,改善其高倍率充放电性能.     

LiODFB基电解液与高电压正极材料LiNi0.5Mn1.5O4的相容性

研究了草酸二氟硼酸锂(LiODFB)基电解液与锂离子电池高电压正极材料锰酸镍锂(LiNi0.5Mn1.5O4)的相容性,结果表明:在25℃和60℃,以LiODFB和六氟磷酸锂(LiPF6)为电解液的LiNi0.5Mn1.5O4/Li电池的CV曲线都具有单一的氧化还原峰,电池的可逆性优良,且LiODFB电池的循环性能优于LiPF6电池。在25℃,LiODFB电池和LiPF6电池以0.5C倍率首次充放电比容量分别为126.3 mAh·g-1、131.6 mAh·g-1,经100次循环后容量保持率分别为97.1%、94.7%;在60℃,LiODFB电池和LiPF6电池以0.5C倍率首次充放电比容量分别为132.6 mAh·g-1、129.1 mAh·g-1,经100次循环后容量保持率分别为94.1%、81.7%。电化学阻抗谱也表明:在60℃,LiODFB电池的阻抗比LiPF6电池的小,LiODFB电池具有更好的高温充放电性能。     

锂离子电池硅炭负极材料的制备与电化学性能研究（英文）

利用微胶囊技术将酚醛树脂包覆于纳米硅表面，然后在氩气保护下高温炭化，制得硅炭复合负极材料。首先采用4种不同质量比的酚醛树脂与纳米硅制备了硅碳复合材料，得到了不同炭质厚度的硅碳复合材料。通过对其循环性能和倍率性能的比较，发现酚醛树脂与纳米硅的质量比为1∶4，即碳层厚度为4.5 nm时，电化学性能最佳。随后对该种硅碳复合材料的综合电化学性能进行了测试，该材料作为负极制备的锂离子电池具有良好的电化学性能，在电流密度为100 mA g^-1的条件下，其首次放电比容量为2 382 mAh g^-1，首次充电比容量为1 667 mAh g^-1，首次库伦效率为70%。经200次充放电循环后放电比容量为835.6 mAh g^-1，库伦效率为99.2%。此外，其倍率性能非常优异，在100、200、500、1 000、2 000及100 mA g^-1电流密度下，其平均放电比容量分别为1 716.4、1 231.6、911.7、676.1、339.8及1 326.4 mAh g^-1...     

锂离子电池硅/碳复合网状整体电极的制备与性能

基于静电喷雾沉积技术制备了硅-纳米炭纤维-石墨烯杂化膜(Si/CNF/G),其中纳米硅颗粒包覆在多孔炭基体中,由纳米硅和多孔炭组成的二次结构被镶嵌在由纳米炭纤维和石墨烯组成的三维交联炭网络中,最终构成无粘结剂的硅/碳复合整体电极。Si/CNF/G三维杂化膜用作锂离子电池电极时,表现高的可逆比容量、长的循环寿命和良好的倍率性能。0.2 A·g~(-1)恒定电流密度下,首次可逆比容量为957mAh·g~(-1),经100圈循环容量保持率为74.4%;2 A·g~(-1)恒定电流密度下,可逆比容量为539mAh·g~(-1)。多孔炭基体可有效缓冲硅的体积变化,促进形成稳定的固态电解质界面;纳米炭纤维和石墨烯构建的三维炭网络既稳定了电极的整体结构,又可为电子和离子提供快速传输通道。     

Low-temperature preparation of polycrystalline silicon from silicon tetrachloride

Polycrystalline silicon has been prepared by zinc reduction of silicon tetrachloride at a low temperature (≈550° C) in a vertical vapour phase reactor. Characterisation of the remelted polycrystalline ingot by X-ray, SEM and electrical methods shows that the material is p-type with an average grain size of 0.5 μm having a room-temperature resistivity in the range 1.0–1.5 Ω cm suitable for solar cell fabrication.     

Photoresponse of hydrogen plasma treated and electron irradiated silicon wafers

Photovoltage (PV) spectra of standard commercial Czochralski n- and p-type silicon wafers with different resistivity subjected to hydrogenation and/or 3.5 MeV electron irradiation have been studied. The PV signal was generated using a band bending present in the wafers. For more information about the influence of hydrogenation and/or electron irradiation on the wafer properties, the measurements of thermo-EMF and surface resistance have been made.The experiments have shown that the hydrogenation of the p-type wafers leads to the appearance of PV signal similar to that for silicon photodiodes as a result of the n-type layer creation near the hydrogenated surface. A drawing field created in the p-type wafers in consequence of their hydrogenation decreases the effect of the carrier diffusion length reduction due to electron irradiation that makes the hydrogenated p-type wafers less sensitive to the radiation impact.     

Gettering of iron in silicon by boron implantation

In this work we studied, both experimentally and theoretically the iron gettering by boron implantation. Sample material was p-type bulk silicon with resistivity of 21 Ωcm. Samples were iron contaminated and boron was implanted into the wafers using two different implantation doses of 4 × 10¹⁵ and 8 × 10¹⁵ cm^?2. After that various gettering annealings were performed. The results indicate that gettering cannot be explained by electronic interactions between interstitial iron and boron ions alone i.e. segregation gettering to heavily doped implantation region. It was found out that better agreement between experimental and simulation results is achieved if heterogeneous precipitation of iron to ion implantation induced damage is included in the simulations. Finally, the effects of high boron doping and gettering site morphology on iron precipitation are discussed.     

Novel thermoelectric materials based on boron-doped silicon microchannel plates

The thermoelectric properties of boron-doped silicon microchannel plates (MCPs) were investigated. The samples were prepared by photo-assisted electrochemical etching (PAECE). The Seebeck coefficient and electrical resistivity at room temperature (25 °C) were measured to determine the thermoelectric properties of the samples. In order to decrease the very high resistivity, boron doping was introduced and by modulating the doping time, a series of samples with different resistivity as well as Seebeck coefficient were obtained. Boron doping changed the electrical resistivity of the samples from 1.5 × 10⁵ Ω cm to 5.8 × 10⁻³ Ω cm, and the absolute Seebeck coefficient deteriorated relatively slightly from 674 μV/K to 159 μV/K. According to the Seebeck coefficient and electrical conductivity, the power factor was calculated and a peak value of 4.7 × 10⁻¹ mW m⁻¹ K⁻² was obtained. The results indicate that silicon MCPs doped with boron are promising silicon-based thermoelectric materials.     

Structural,optical and electrical properties of SnO<Subscript>2</Subscript>:F thin films deposited by spray pyrolysis for application in thin film solar cells

Fluorine doped tin oxide (FTO) thin films with adequate properties to be used as transparent electrical contact for PV solar cells were synthesised using the spray pyrolysis technique, which provides a low cost operation. The deposition temperature and the fluorine doping have been optimized for achieving a minimum resistivity and maximum optical transmittance. No post-deposition annealing treatments were carried out. The X-ray diffraction study showed that all the FTO films were polycrystalline with a tetragonal crystal structure and preferentially oriented along the (200) direction. The grain size ameliorates with the increase in substrate temperature. The samples deposited with the substrate temperature at 440 °C and fluorine content of 20 wt % exhibited the lowest electrical resistivity (1.8 × 10^?4 Ω cm), as measured by four-point probe. Room-temperature Hall measurements revealed that the 20 wt% films are degenerate and exhibit n-type electrical conductivity with carrier concentration of ~4.6 × 10²⁰ cm^?3, sheet resistance of 6.6 Ω/□ and a mobility of ~25 cm² V^?1 s^?1. In addition, the optimized growth conditions resulted in thin films (~500 nm thickness) with average visible transmittance of 89 % and optical band-gap of 3.90 eV. The electrical and optical characteristics of the deposited films revealed their excellent quality as a TCO material.     

Temperature Measurement of Semitransparent Silicon Wafers Based Upon Absorption Edge Wavelength Shift

The temperature dependence of silicon wafer transmittance is well understood, and is caused by various absorption mechanisms over a wide spectral range. As the wavelength increases, the photon energy decreases until it becomes lower than the minimum energy gap in the silicon band structure. At this point, which is often referred to as the absorption edge wavelength, there is a rapid drop in absorption. The absorption edge shifts to a longer wavelength with increasing temperature, because the bandgap narrows with increasing temperature. Experiments were carried out with varying wavelength (900 nm to 1700 nm), polarization (p- and s-polarized), and direction (from normal to 80°), using specimens with different resistivities (0.01 Ω · cm to 2000 Ω · cm). A characteristic curve relating the absorption edge wavelength and temperature was obtained for all of the silicon wafers, despite their differing resistivity. This method enables in situ temperature measurements of silicon wafers from room temperature to 900 K, using wavelengths to which the wafer is semitransparent. In this article, an experimental apparatus and measurement results are described in detail, and several remaining problems are discussed.     

Electrical and optical properties of TOS-S heterojunction devices

Photoelectrical properties of heterojunctions based on transparent oxide semiconductor (TOS) thin films-semiconductor (S) are outlined. The structures consisted of transparent thin films of TiO₂ doped with V and Pd (n-type semiconductor) and TiO₂ with Co and Pd (p-type semiconductor) deposited by magnetron sputtering on standard silicon wafers (p-type and n-type respectively). The structures were examined by means of current-voltage (I-V) measurements and the Optical Beam Induced Current (OBIC) method. Temperature dependent I-V characteristics displayed a strong non-linear behaviour of prepared TOS-S heterojunctions.     

Thermoelectric properties of SiC thick films deposited by thermal plasma physical vapor deposition

SiC thick films of about 300 µm could be prepared with a deposition rate above 300 nm/s by thermal plasma physical vapor deposition (TPPVD) using ultrafine SiC powder as a starting material. The thermoelectric properties were investigated as a function of composition and doping content. The nondoped films showed n-type conduction. Although the Seebeck coefficient reached as high as -480 µV/K, the power factor was only around 1.6 × 10^-4 Wm^-1 K^-2 at 973 K due to the relatively high electrical resistivity. In order to reduce the electrical resistivity and to deposit layers with n-type and p-type conduction, N₂, B and B₄C were selected as the dopants. Nitrogen-doped samples exhibit n-type characterization, B and B₄C-doped samples exhibit p-type characterization, and the electrical resistivity decreased from 10^-2–10^-3 to 10^-4–10^-5 Ωm after doping. The maximum power factor of the nitrogen-doped SiC and the thick films deposited with B₄C powder reached 1.0 × 10^-3 and 6.4 × 10^-4 Wm^-1 K^-2 at 973 K, respectively.

© 2003 Elsevier Science Ltd. All rights reserved.     

非晶硅太阳电池窗口层材料掺硼非晶金刚石的研究

以固态掺杂方式利用过滤阴极真空电弧技术制备掺硼非晶金刚石薄膜, 获得性能优良的宽带隙p型半导体材料, 再利用等离子增强化学气相沉积技术制备p-i-n结构非晶硅太阳电池的本征层和n型层, 最终制成以掺硼非晶金刚石薄膜为窗口层的非晶硅太阳电池. 利用Lambda950紫外-可见光分光光度计表征薄膜的光学带隙, 并测试电池开路电压、短路电流、填充因子以及转化效率等参数, 再分析电池的光谱响应特性. 实验表明, 掺硼非晶金刚石薄膜的光学带隙(～2.0eV)比p型非晶硅更宽, 以掺硼非晶金刚石薄膜用作非晶硅太阳电池的窗口层, 能够改善电池的光谱响应特征, 并提高转化效率达10%以上.     

醇盐直接煅烧法制备ATO纳米粉体的研究

将SnCl2·2H2O和SbCl3分别溶解在无水乙醇中,再将SbCl3乙醇溶液分散到SnCl2乙醇溶液中,蒸干后得到醇盐粉体,然后通过直接煅烧醇盐的方法制备了纳米级ATO粉体,运用XRD、DSC等手段对制得的ATO粉体进行了表征,考察了Sb掺杂量对所得纳米粉体导电性能的影响,研究发现,当锑在ATO粉体中的摩尔比为6%时,电阻率最小为11.42Ω·cm;当掺杂量为15%时,制得的粉体粒径主要分布在50nm-100nm范围内。