Fe2O3纳米纤维锂离子电池负极材料的制备及其电化学性能研究

Fe₂O₃具有理论比容量高和价格低廉等特点, 已成为锂离子电池负极材料的研究热点之一。实验以不同质量比PVP/FeCl₃溶液为前驱体, 静电纺丝技术制备PVP/FeCl₃纳米纤维并热处理, 得到不同直径的Fe₂O₃纳米纤维负极材料, 并以水热合成法制备了Fe₂O₃纳米颗粒。利用X射线衍射、热重、红外光谱、扫描电镜、透射电镜和恒流充放电等测试手段对材料的物相、微观形貌和电化学性能进行表征。结果表明, Fe₂O₃纳米纤维比Fe₂O₃纳米颗粒表现出更优的电化学性能, 直径为160 nm的Fe₂O₃纳米纤维负极材料的倍率性能和循环性能最佳, 材料在0.1 A/g电流密度下的可逆容量为827.3 mAh/g;在2 A/g电流密度下70次循环放电比容量有439.1 mAh/g。     

负热膨胀材料对微米硅负极的改性研究

通过溶胶-凝胶法和高温固相法，将负热膨胀材料ZrV₂O₇包覆在硅微粉表面。结果表明：负热膨胀材料ZrV₂O₇能有效地改善界面稳定性，提升循环性能。当与碳材料进一步结合，构建C-ZrV₂O₇复合包覆层时，发现负热膨胀材料和碳具有协同作用。C-ZrV₂O₇包覆层在循环过程中与硅结合得更紧密，从而有效地抑制了硅负极与电解液的反应。改性后的材料有更高的可逆比容量和循环稳定性，在0.1C的放电倍率下，循环120周后放电比容量仍能稳定在500mAh/g以上，接近于纳米硅材料，显示出一定的工业应用价值。     

超临界CO2流体辅助合成Si-Fe-Fe3O4-C复合材料及储锂性能

硅碳负极是未来锂离子电池材料发展的重点方向之一,本文针对传统球磨法制备硅碳负极复合不均匀、界面融合差等问题,提出了一种超临界二氧化碳(scCO₂)流体介质球磨合成Si-Fe-Fe₃O₄-C复合材料的新方法。研究发现,纳米硅和中间相碳微球(MCMB)在scCO₂介质球磨混合过程中,CO₂和Fe反应先得到均匀分散的Si-FeCO₃-C前驱体,然后FeCO₃原位高温固相分解得到Si-Fe-Fe₃O₄-C复合材料。同时,在scCO₂流体渗透下,MCMB剥离成石墨片,并与纳米硅和Fe-Fe₃O₄实现较好的界面融合,Fe-Fe₃O₄的引入显著提升了硅碳负极的储锂容量、循环稳定性和倍率性能,Si-Fe-Fe₃O₄-C复合材料在0.2 A·g?1下100次循环后可逆容量保持在1065 mA·h·g?1。本方法利用超临界流体渗透性好、扩散能力强等特点,合成工艺简便,容易工业化实施,具有商业化开发潜力。      

高性能自支撑不锈钢网@MoS2锂离子电池负极材料

为了提高MoS₂作为Li离子电池负极材料整体的导电性和稳定性,将纳米化的MoS₂与其它导电性好的材料进行复合,通过水热法在导电基底不锈钢网(Stainless steel net, SS)上原位合成了一层MoS₂纳米花,制备了无粘结剂的自支撑结构的SS@MoS₂负极材料。纳米花状的MoS₂和导电性优异的SS提高了电子和Li离子的扩散速率,同时改善了电极的反应动力学。当作为Li离子电池负极材料时,SS@MoS₂电极表现出优异的储Li性能,特别是具有显著的大倍率充放电性能,即在1 000 mA/g的大电流密度下循环600次,比容量仍保持在862.1 mA·h/g。      

壳聚糖衍生碳包覆纳米硅复合材料锂离子电池性能研究

硅负极材料因具有较高的理论容量(Li₂₂Si₅合金相对应4 200 mAh/g)、较低的工作电压(0.2～0.3 V vs Li/Li⁺)和地球上丰富的原材料储备,成为代替石墨负极的理想材料之一。但是,低电导率及在循环过程中发生剧烈体积膨胀导致电极失效问题限制了硅负极材料的进一步发展。因此,本工作通过物理法利用壳聚糖和石墨对纳米硅实现碳包覆和复合,制备壳聚糖/石墨@纳米硅复合材料(C/G@Si复合材料),对C/G@Si复合材料的结构、形貌和电化学性能进行研究。结果表明：随着石墨添加量的提高,C/G@Si复合材料的可逆比容量略微下降,循环性能和导电性能显著提高。当添加50%(质量分数)石墨时,在100 mA/g的电流密度下,C/G@Si复合材料的首次放电比容量为1 136.1 mAh/g,循环充放电100次后剩余容量保持在658.5 mAh/g,展示出优异的电化学性能,对进一步推广硅碳负极材料具有一定的参考价值。     

将硅纳米颗粒限域在多壳层空心球:一种提升循环稳定性的有效策略（英文）

单质硅是一种有潜力的高容量锂离子电池负极材料.然而,受限于充放电过程中巨大的体积膨胀,其循环性能并不理想.在这个工作中,我们设计了一种独特的三组分复合负极材料(Si/Cr₂O₃/C),其中Si纳米颗粒被限域在碳包覆的氧化铬多层空心球(MSHSs)中.得益于Cr₂O₃/C基体的体积变化缓冲能力与优异的结构稳定性,将Si纳米颗粒封装在MSHSs中可以有效地提高其电化学性能.合理的结构设计赋予了Si/Cr₂O₃/C三组分复合材料高的可逆容量(在100 mA g^-1的电流密度下,比容量为1351 mA h g^-1)和稳定的循环性能(在500 mA g^-1的电流密度下,循环300次后比容量保持在716 mA h g^-1).这一工作提出了一种多壳层空心结构设计的新思路,以解决硅基负极材料循环性差的瓶颈.     

ZnO@Mo-CNT-MnO2纳米阵列用于构筑超高倍率性能的柔性非对称超级电容器(英文)

MnO₂作为超级电容器电极材料具有理论比电容高、成本低、环境友好等优点,但其低导电性和低利用率阻碍了其潜在应用.本研究首先在柔性碳布上电化学生长ZnO纳米棒阵列作为电极衬底,然后通过阳极电沉积法在ZnO纳米棒阵列表面外延生长了Mo和碳纳米管(CNTs)共掺杂的MnO₂薄膜,可控构筑了有效、高导电性的MnO₂纳米阵列电极(定义为ZnO@Mo-CNT-MnO₂ NA).柔性ZnO@Mo-CNTMnO₂ NA电极在100 A g^-1的大电流充放电密度下比电容可达237.5 F g^-1,10,000次循环后电容保留率高达86%.采用ZnO@Mo-CNTMnO₂ NA电极组装成水系非对称超级电容器,弯曲状态下在132.35 mW cm^-3(5mA cm^-2)高功率密度下获得了1.13 mW h cm^-3的高能量密度,5mA cm^-2充放...     

硅化镁还原CO2一步原位合成Si/C复合负极

硅碳(Si/C)负极被认为是高能量密度锂离子电池的首选负极材料,本文提出了一种利用Mg₂Si一步还原CO₂原位制备硅碳复合材料的新方法,研究了Ar∶CO₂混合气体积比和反应温度等关键工艺对Si/C负极材料微结构和电化学性能的影响。研究发现,该方法原位合成的Si/C颗粒尺寸为几百纳米,晶态硅和无定形碳相互交织、分布均匀。当反应温度为700℃、Ar∶CO₂=7∶1时合成的Si/C复合材料作为锂离子电池负极材料时,在0.2 A/g的电流密度下,500个循环后仍有1134 mA·h/g可逆容量。本文利用温室气体CO₂来制备储能用Si/C复合负极材料,既能实现变废为宝,同时该方法合成工艺简便,容易工业化实施,具有商业化开发的潜力。      

聚吡咯包覆导电炭黑/氧化铟复合材料的制备及其在铅酸电池中的应用

为了改善铅酸电池负极不可逆硫酸盐化及析氢问题,通过原位化学聚合的方法制备导电炭黑/氧化铟表面包覆聚吡咯[PPy@(C/In₂O₃)]复合材料,采用SEM、FTIR、BET和XRD等表征手段分别对复合材料的微观形貌和结构进行分析;通过循环伏安法(CV)和线性扫描法(LSV)测试了复合材料的电化学性能。最后,将PPy@(C/In₂O₃)复合材料添加到铅酸电池负极活性材料中,探究PPy@(C/In₂O₃)对铅酸电池高倍率部分荷电状态(HRPSoC)循环寿命及放电容量的影响。结果表明：PPy@(C/In₂O₃)保留了导电炭黑的基本结构特征,具有较大比表面积;同时具有较高析氢过电位及较大比容量。当将PPy@(C/In₂O₃)复合材料添加到铅酸电池负极活性材料中,不仅可以降低负极板内阻抑制电池的负极硫酸盐化问题,而且可以减弱电池负极析氢问题,在提高铅酸电池放电容量同时,显著提高了铅...     

高性能自支撑CuS/SnS2锂电池负极材料

过渡金属硫化物作为锂电池负极材料具有极高比容量,但其制备的电极普遍存在导电性差、体积变化大等问题,本研究设计了一种新型的自支撑CuS/SnS₂镂空片状锂电池负极材料,以导电碳布作为基底,生长包覆CuS/SnS₂镂空纳米片,具备特殊的纳米包覆结构及双金属协同效应,使其在保持较高比容量的同时具备良好的循环稳定性,整体电化学性能优异。研究不同Cu/Sn含量对CuS/SnS₂负极材料电化学性能的影响,最佳配比的CuS/SnS₂负极材料在0.2 A·g?1电流密度下循环50次后比容量为1480 mAh·g?1,库伦效率稳定在99.5%,在2 A·g?1电流密度下循环200次后比容量仍能保持在697 mAh·g?1,库伦效率为99.8%。      

交替刻蚀制备有序锯齿形硅纳米线阵列及其光学性能研究

采用金属催化化学刻蚀法(MCCE),以金属Ag为催化剂,在HF与H2O2体系中通过交替刻蚀在P(111)硅衬底上制备出锯齿形硅纳米线阵列.利用扫描电子显微镜对硅纳米线的形貌进行了表征,研究了HF浓度与H2O2浓度对纳米线刹蚀方向的调控作用.选取不同的HF与H2O2浓度配比,分别对硅基底各向同性刻蚀与各向异性刻蚀进行调控,使得刻蚀方向对溶液浓度的变化能够快速响应.在溶液Ⅰ([HF]=2.3 mol/L,[H2O2]=0.4 mol/L)与溶液Ⅱ([HF]=9.2 mol/L,[H2O2]=0.04 mol/L)中交替刻蚀,制备出刻蚀方向高度可控的大规模锯齿形硅纳米线.利用紫外-可见分光光度计对锯齿形硅纳米线的减反射性能进行研究,结果表明,其表现出优异的减反特性,最低反射率为5.9％.纳米线形貌的高度可控性使其在微电子器件领域也具有巨大的应用前景.     

Unveiling the formation pathway of single crystalline porous silicon nanowires

Porous silicon nanowire is emerging as an interesting material system due to its unique combination of structural, chemical, electronic, and optical properties. To fully understand their formation mechanism is of great importance for controlling the fundamental physical properties and enabling potential applications. Here we present a systematic study to elucidate the mechanism responsible for the formation of porous silicon nanowires in a two-step silver-assisted electroless chemical etching method. It is shown that silicon nanowire arrays with various porosities can be prepared by varying multiple experimental parameters such as the resistivity of the starting silicon wafer, the concentration of oxidant (H(2)O(2)) and the amount of silver catalyst. Our study shows a consistent trend that the porosity increases with the increasing wafer conductivity (dopant concentration) and oxidant (H(2)O(2)) concentration. We further demonstrate that silver ions, formed by the oxidation of silver, can diffuse upwards and renucleate on the sidewalls of nanowires to initiate new etching pathways to produce a porous structure. The elucidation of this fundamental formation mechanism opens a rational pathway to the production of wafer-scale single crystalline porous silicon nanowires with tunable surface areas ranging from 370 to 30 m(2) g(-1) and can enable exciting opportunities in catalysis, energy harvesting, conversion, storage, as well as biomedical imaging and therapy.     

Integrated freestanding single-crystal silicon nanowires: conductivity and surface treatment

Integrated freestanding single-crystal silicon nanowires with typical dimension of 100 nm × 100 nm × 5 μm are fabricated by conventional 1:1 optical lithography and wet chemical silicon etching. The fabrication procedure can lead to wafer-scale integration of silicon nanowires in arrays. The measured electrical transport characteristics of the silicon nanowires covered with/without SiO(2) support a model of Fermi level pinning near the conduction band. The I-V curves of the nanowires reveal a current carrier polarity reversal depending on Si-SiO(2) and Si-H bonds on the nanowire surfaces.     

Patterning of various silicon structures via polymer lithography and catalytic chemical etching

We demonstrate a facile fabrication of a rich variety of silicon patterns with different length scales by combining polymer lithography and a metal-assisted chemical etching method. Several types of polymer patterns were fabricated on silicon substrates, and silver layers were deposited on the patterned silicon surfaces and used to etch the silicon beneath. Various silicon patterns including topographic lines, concentric rings, and square arrays were created at a micro-?and nanoscale after etching the silicon and subsequent removal of the patterned polymer masks. Alternatively, the arrays of sub-30?nm silicon nanowires were produced by a chemical etching of the silicon wafer which was covered with highly ordered polystyrene-block-polyvinylpyridine (PS-b-PVP) micellar films. In addition, silicon nanohole arrays were also generated by etching with hexagonally packed silver nanoparticles that were prepared using PS-b-PVP block copolymer templates.     

电催化金属辅助化学刻蚀法制备硅纳米线/多孔硅复合结构

量子限制效应使硅纳米线具有良好的场致发射特性,结合多孔硅的准弹道电子漂移模型可提高场发射器件的性能.传统的金属辅助化学刻蚀法制备硅纳米线的效率较低,本研究在传统方法的基础上引入恒流源,提出电催化金属辅助化学刻蚀法,高效制备了硅纳米线/多孔硅复合结构.在外加30 mA恒定电流的条件下,硅纳米线的平均制备速率可达308 n...     

Effect of electroless etching parameters on the growth and reflection properties of silicon nanowires

Vertically aligned silicon nanowire (Si NW) arrays have been fabricated over large areas using an electroless etching (EE) method, which involves etching of silicon wafers in a silver nitrate and hydrofluoric acid based solution. A detailed parametric study determining the relationship between nanowire morphology and time, temperature, solution concentration and starting wafer characteristics (doping type, resistivity, crystallographic orientation) is presented. The as-fabricated Si NW arrays were analyzed by field emission scanning electron microscope (FE-SEM) and a linear dependency of nanowire length to both temperature and time was obtained and the change in the growth rate of Si NWs at increased etching durations was shown. Furthermore, the effects of EE parameters on the optical reflectivity of the Si NWs were investigated in this study. Reflectivity measurements show that the 42.8% reflectivity of the starting silicon wafer drops to 1.3%, recorded for 10 μm long Si NW arrays. The remarkable decrease in optical reflectivity indicates that Si NWs have a great potential to be utilized in radial or coaxial p-n heterojunction solar cells that could provide orthogonal photon absorption and enhanced carrier collection.     

密度可控的TiO2纳米线束阵列合成及其在量子点敏化太阳能电池上的应用

采用水热合成技术, 以盐酸、去离子水和钛酸丁酯为反应前驱物, 直接在透明导电玻璃(FTO)衬底上合成了具有金红石结构的TiO₂纳米线束阵列。通过改变反应前驱物中钛酸丁酯的添加量, 实现了对TiO₂纳米线束阵列密度的调控。以TiO₂纳米线束阵列为光阳极、CdS为敏化剂, 组装了量子点敏化太阳能电池器件, 并研究了纳米线束阵列的密度对电池光伏性能的影响。结果表明: 纳米线的密度过高或过低均不利于电池光伏性能的提高。纳米线的优化密度为11.8×10⁶ /mm², 此时电池的光电转换效率达到了0.947%。     

一种链珠状SiO2纳米线的制备及分析

实验通过硅粉和氯化钙盐高温处理, 以熔融CaCl₂高温下产生的蒸气作为特殊的蒸发载体, 在1300℃条件下通过热蒸发法在石墨基板表面获得了具有草坪状排列的特殊形状的纳米线。系列测试分析表明, 该纳米线的直径为50~400 nm, 长度约为几个微米, 且为面心立方结构。另外, 系统分析显示传统的纳米线生长模型如气-液-固(VLS)生长机制不能很好地解释该二氧化硅纳米线在石墨纸上的生长过程, 本文提出的一种增强的气-液-固生长机制, 可以很好地解释上述纳米线的生长过程。     

Porosity control in metal-assisted chemical etching of degenerately doped silicon nanowires

We report the fabrication of degenerately doped silicon (Si) nanowires of different aspect ratios using a simple, low-cost and effective technique that involves metal-assisted chemical etching (MacEtch) combined with soft lithography or thermal dewetting metal patterning. We demonstrate sub-micron diameter Si nanowire arrays with aspect ratios as high as 180:1, and present the challenges in producing solid nanowires using MacEtch as the doping level increases in both p- and n-type Si. We report a systematic reduction in the porosity of these nanowires by adjusting the etching solution composition and temperature. We found that the porosity decreases from top to bottom along the axial direction and increases with etching time. With a MacEtch solution that has a high [HF]:[H(2)O(2)] ratio and low temperature, it is possible to form completely solid nanowires with aspect ratios of less than approximately 10:1. However, further etching to produce longer wires renders the top portion of the nanowires porous.     

金刚石线锯切割多晶硅片表面制绒工艺研

晶体硅片的制绒技术是太阳能电池制造工艺中的关键步骤。本研究以工业中酸制绒方法为基础, 研究了腐蚀时间、浓度对绒面结构以及反射率的影响。此外, 还采用金属催化化学腐蚀法进行制绒, 选用氢氟酸和硝酸银作为腐蚀液。而且对两种制绒方法效果进行了对比。研究获得的最优绒面结构及反射率结果的实验条件为: 氢氟酸浓度4.6 mol/L、硝酸银浓度0.02 mol/L, 室温下反应90 min, 得到的平均反射率为8%, 远低于目前多晶硅片制绒生产标准。