交联孔隙结构TiO_2-PEDOT:PSS纳米复合薄膜的制备及作为对电极的应用

以TiO2为多孔模板并以聚3,4-亚乙二氧基噻吩-聚苯乙烯磺酸(PEDOT:PSS)为催化材料合成了具有交联孔隙结构的TiO2-PEDOT:PSS纳米复合薄膜(TPNF),并将其作为对电极应用于染料敏化太阳电池(DSC)。首先将TiO2纳米颗粒沉积在导电的掺杂氟的SnO2透明玻璃(FTO)上形成骨架和孔隙均在纳米级别的模板,随后将PEDOT:PSS水溶液附着在模板的骨架表面,最终经热处理获得TPNF。通过优化模板结构和旋涂转速,获得了催化活性优异的TPNF,组装后DSC的填充因子和转换效率分别达到0.528和4.57%,均远高于纯PEDOT:PSS薄膜组装的器件的填充因子(0.297)和转换效率(1.98%)。改善的光电性能归功于TPNF具有优异的协同效应:导电的TiO2骨架为电子迁移提供了快速路径,同时涂覆在骨架表面的PEDOT:PSS通过扩展表面积为还原电解质提供了更多的催化活性点。     

锐钛矿相TiO2纳米管的制备及其染科敏化太阳电池

以商用金红石相TiO2粉末为原料,通过在碱性溶液中150℃水热48h的方法合TiO2纳米管.采用SEM,TEN,XRD分析手段对TiO2纳米管的形貌和结构演变进行了表征.制成的TiO2纳米管与TritonX-100,乙酰丙酮混合后,通过丝网印刷的方法涂敷到ITO导电玻璃衬底上,并且在450℃下烧结30min后得到可应用于染料敏化太阳电池的多孔光阳极.将此光阳极浸泡于N719染料敏化后,与镀铂对电极组装电池,两者之间灌入液态电解质,电池的有效面积为0.28 cm2.在标准氙灯模拟器下(AM 1.5,100 roW/cm2)测试r电池的J-V特性,得到2.17%的光电转换效率.     

TiO_2对α-Fe_2O_3纳米微粒拉曼散射效应的影响

选取α Fe2O3和TiO2研究一种氧化物对另一种氧化物的拉曼散射效应。采用Sol gel方法制备纳米α Fe2O3/TiO2复合微粒,α Fe2O3粒径及含量分别为20nm、150nm和3%、6%、12%。制备过程中调节水解时的pH值和热处理温度,得到掺杂α Fe2O3粒子的不同晶型的TiO2纳米颗粒。Raman测量结果显示,α Fe2O3粒径越小、含量越高,TiO2对其散射效应的影响越大。不同的TiO2晶型对α Fe2O3纳米粒子的拉曼增强效应也不同。锐钛矿型及金红石型TiO2对α Fe2O3有一定的拉曼增强作用,当水解pH值较小时,得到板钛矿型TiO2,由于部分板钛矿型TiO2振动声子模的峰位与α Fe2O3的重叠,所以尚难观察它对α Fe2O3的拉曼增强效应。     

Al2O3-H2O纳米流体的相变蓄冷实验研究

通过在水介质中添加纳米氧化铝粒子,研制了一种新型传热冷却工质一氧化铝-水纳米流体,粒径分布显示了加入分散剂的悬浮液具有很好的分散性,同时对Al2O3-H2O纳米流体和水溶液的结冰过程进行了实时观察.结果表明,加入Al2O3纳米粒子后,流体的结冰速率得到了很大提高,结冰时间大大缩短,DSC测试结果得到0.1%Al2O3-H2O纳米流体的相变潜热值为313.1 J/g.     

弱旋湍流火焰合成纳米二氧化钛的机理研究

湍流效应在火焰合成纳米TiO2颗粒工业化规模放大中具有重要影响.本文基于一种内加环形旋流片的弱旋火焰开展了合成TiO2纳米颗粒的实验研究.对于内径12 mm管式燃烧器,加入旋片后火焰贫燃极限大幅度降低16%～33%,火焰高度也从9.0 cm减少到3.0 cm,焰区温度约减少20%～30%.研究表明,弱旋湍流火焰具有流速大、可燃当最比低和温度低的特点,使其相对无旋火焰可以合成粒径较小、烧结程度较低的TiO2纳米颗粒.     

载铈纳米TiO2粉体的制备及其反射光谱特性研究

采用金属离子组装技术对纳米TiO2进行了稀土元素铈的负载,借助X射线衍射和透射电子显微镜对载铈纳米TiO2粉体进行了表征,并用紫外-可见光漫反射光谱法对载铈前后纳米TiO2粉体的反射光谱特性进行了分析。结果发现：稀土元素铈负载后,纳米TiO2的反射光谱特性向可见光方向移动,红移到了500nm;并且在可见光区域的吸光率也发生了明显变化,提高了3倍。表明稀土元素铈的负载有利于提高纳米锐钛矿型TiO2对可见光和紫外光的吸收,从而大幅度提高其光催化活性。     

TiO2颗粒尺寸对染料敏化太阳电池内电子输运特性影响研究

采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)研究了染料敏化太阳电池(DSC)内部电子传输和背反应动力学特性.在纳米TiO2薄膜厚度相同的情况下,借助于IMPS/IMVS测量了由3种不同TiO2颗粒尺寸大小薄膜制备出DSC的电荷传输特征参数值.IMPS/IMVS理论模型拟合实验测量数据的结果表明:在不同入射光强下,随着颗粒尺寸的增大,电子扩散系数(Dn)增大,而电子寿命(τn)减小,电子传输时间(τd)也减小.Dn随颗粒尺寸增大而增加归因于薄膜表面积的减小,而τn减小可以通过缺陷之间的跃迁频率来解释,τd减小是由于TiO2薄膜内缺陷浓度减小而导致的.     

稀土Eu3+掺杂纳米TiO2-SiO2发光材料的制备和发光性质的研究

采用溶胶-凝胶法制备了稀土Eu3+掺杂于不同比例的纳米TiO2-SiO2复合体系,研究了基质中钛、硅摩尔配比对发光性能的影响.样品的FTIR谱图显示:纳米复合氧化物SiO2-TiO2之间发生了键合作用,形成了Ti-O-Si键;TEM显示样品的颗粒大小约为35 nm,是具有一定的单分散性的球形颗粒;XRD和SAED结果表明,样品退火至700℃后仍为单一的锐钛矿相,这说明微量硅的加入对二氧化钛的锐钛矿相有热稳定的作用.当微量的Si4+进入TiO2的晶格,取代部分Ti4+的位置时,形成了结构等电子陷阱.通过对样品的激发光谱、发射光谱分析,发现这种结构有利于将基质吸收的能量传递到发光中心,使Eu3+的465nm处7F0→5D2激发效率最高,成为最灵敏的激发线.     

用SAXS和XRD方法研究Ti02纳米颗粒微观结构

用溶胶一凝胶方法制备了TiO2纳米样品.并对该样品在300℃到800℃温度区域进行了退火处理.应用同步辐射x射线粉未衍射(XRD)方法研究了经不同热处理温度的TiO2纳米颗粒的结构相变.应用同步辐射小角x射线散射(SAXS)方法研究了TiO2纳米颗粒的表面分形与界面特性.得到纳米颗粒粒度与退火温度的变化规律,讨论r表面界面特征与相变的关系.     

纳米TiO2多孔膜的微结构对染料敏化纳米薄膜太阳电池性能的影响

采用溶胶-凝胶方法，在不同的实验条件下获得平均粒径从15到25nm左右的纳米TiO２2颗粒.利用这些颗粒制备出的纳米多孔薄膜，应用于染料敏化纳米薄膜太阳电池. 通过x射线 衍射仪分析，得到TiO２₂颗粒的晶相以及晶粒度大小，用透射电子显微镜观察 了纳米TiO２₂颗粒的形貌和尺寸.应用于太阳电池的纳米TiO２₂多 孔膜，经基于布朗诺尔-埃米特-泰 勒（BET）的多层吸附理论的比表面积测试和孔径分布测试，获得了多孔膜的微 关键词： 溶胶-凝胶法 2')" href="#">纳米TiO２₂ 染料敏化 太阳电池     

无锂助熔剂B_2O_3对Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3固体电解质离子电导率的影响

采用固相法制备锂离子电池用固体电解质磷酸钛锂铝Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3(LATP),研究了不同烧结温度以及助熔剂对LATP固体电解质离子电导率的影响.采用X射线衍射、能谱分析、扫描电镜和交流阻抗等方法,研究样品的结构特征、元素含量、形貌特征以及离子导电性能.结果表明,在900?C烧结可以获得结构致密、离子电导率较高的纯相LATP陶瓷固体电解质.与添加助熔剂Li BO2的样品进行对比实验发现,采用B_2O_3代替LiBO_2作为助熔剂也可以提高烧结样品的离子电导率,并且电解质的离子电导率随助熔剂添加量的增大,先增大后减小,其中添加质量百分比为2%的B_2O_3的样品具有最高的室温离子电导率,为1.61×10~(-3)S/cm.     

Investigation on the effects of addition of SiO<Subscript>2</Subscript> nanoparticles on ionic conductivity,FTIR, and thermal properties of nanocomposite PMMA–LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>

Composite polymer electrolyte systems composed of poly(methyl methacrylate) (PMMA) as the host polymer, lithium trifluoromethanesulphonate (also known as lithium triflate; LiCF₃SO₃) as dopant salt, and a variety of different concentrations of nano-sized fumed silica (SiO₂) as inorganic filler were studied. The effect upon addition of SiO₂ on the ionic conductivity of the composite polymer electrolytes was investigated, and it was proven that the ionic conductivity had been enhanced. In addition, the interfacial stability also showed improvement. Maximum conductivity was obtained upon addition of 2 wt.% SiO₂. The complexation of PMMA and LiCF₃SO₃ was verified through Fourier transform infrared studies. The thermal stability of the polymer electrolytes was also found to improve after dispersion of inorganic filler. This was proven in the thermogravimetric studies.     

Nonlinear ion transport in liquid and solid electrolytes

This paper describes nonlinear ion transport properties of liquid and solid electrolytes. Typically, the relation between ionic current density and electric field becomes nonlinear at electric fields above 50–100?kV/cm. We review the 1st and 2nd Wien effect found in classical strong and weak electrolyte solutions as well as the strong nonlinear ion transport effects observed for inorganic glasses and for polymer electrolytes. Furthermore, we give an overview over models describing nonlinear ion transport in electrolyte solutions, in glasses and in polymers. Recent results are presented for the nonlinear ionic conductivity of supercooled ionic liquids. We show that supercooled ionic liquids exhibit anomalous Wien effects, which are clearly distinct from the classical Wien effects. We also discuss the frequency dependence of higher-order conductivity and permittivity spectra of these liquids.     

Hydroxyl terminated Poly(dimethylsiloxane) as an electrolyte additive to enhance the cycle performance of lithium-ion batteries

Hydroxyl terminated poly(dimethylsiloxane) (PDMS-HT) is used as an electrolyte additive in electrolyte systems containing 1 M LiPF₆ in EC:DMC (ratios 1:9; 3:7; 4:6 and 1:1 v/v) to enhance the cycle performance of lithium-ion batteries. Adding a small amount of PDMS-HT to the standard LIB electrolyte leads to improved specific capacity as well as improved capacity retention over prolonged cycles. There is also a slight increase in Li⁺ ion conductivity when PDMS-HT is added. Also, the PDMS-HT additive allows the formation of a more stable solid electrolyte interface (SEI) layer that enables the LIB cells to be cycled for longer cycles with minimal capacity fading. This combination of improved ionic conductivity and stable SEI layer formation due to the PDMS-HT additive, makes it an excellent candidate for an electrolyte additive for lithium ion batteries.     

A piperidinium-based ionic liquid electrolyte to enhance the electrochemical properties of LiFePO<Subscript>4</Subscript> battery

A piperidinium-based ionic liquid, N-methylpiperidinium-N-acetate bis(trifluoromethylsulfonyl)imide ([MMEPip][TFSI]), was synthesized and used as an additive to the electrolyte of LiFePO₄ battery. The electrochemical performance of the electrolytes based on different contents of [MMEPip][TFSI] has been investigated. It was found that the [MMEPip][TFSI] significantly improved the high-rate performance and cyclability of the LiFePO₄ cells. In the optimized electrolyte with 3 wt% [MMEPip][TFSI], 70 % capacity can be retained with an increase in rate to 3.5 C, which was 8 % higher than that of electrolyte without [MMEPip][TFSI]. For the Li/LiFePO₄ half-cells, after 100 cycles at 0.1 C, the discharge capacity retention was 78 % in the electrolyte without ionic liquid. However, in the electrolyte with 3 wt% [MMEPip][TFSI], it displayed a high capacity retention of 91 %. The good electrochemical performances indicated that the [MMEPip][TFSI] additive would positively enhance the electrochemical performance of LiFePO₄ battery.     

Ionic liquid enhanced magnesium-based polymer electrolytes for electrical double-layer capacitors

This paper describes the preparation and characterization of poly(vinyl alcohol) (PVA)-added ionic liquid-based ion conductors. The polymer electrolyte is incorporated with magnesium triflate [Mg(CF₃SO₃)₂ or MgTf] as salt and 1-butyl-3-methylimidazolium bromide (BmImBr) as ionic liquid. Differential scanning calorimetry (DSC) is carried out to investigate the glass transition temperature which is used to study the plasticizing effect of the ionic liquid. The highest conducting ionic liquid-based polymer electrolyte is used to fabricate electrical double-layer capacitors (EDLC). The electrochemical potential window is evaluated using linear sweep voltammetry (LSV). The electrochemical capacitance of the EDLC is evaluated through cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD). The electrochemical potential window of ionic liquid-added polymer electrolyte is extended from 1.35 to 2.6 V. Cyclic voltammetry (CV) proves the improvement in specific capacitance of the electrical double-layer capacitors (EDLCs) containing ionic liquid-added polymer electrolyte.     

Preparation and characterization of a special structural poly(acrylonitrile)-based microporous membrane for lithium-ion batteries

In this work, a special structural poly(acrylonitrile) (PAN)-based microporous membrane for lithium-ion batteries is prepared from PAN emulsion by simple casting and extracting techniques. It is found that the microporous membrane is fabricated by PAN particles with uniform size (about 580 nm), and a lot of micropores exist among the particles. The Gurley number of the microporous membrane obviously depends on the amount of additive but the porosity does not. The PAN-based microporous membrane is activated by non-aqueous liquid electrolyte to form microporous gel electrolyte (MGE), and its ionic conductivity increases with the decrease of the Gurley number. The resulting MGE shows typical thermal shut-down action because of the swelling–incorporating behaviors of PAN-based particles by the help of the solvent of liquid electrolyte at high temperature. In addition, the electrochemical stability window of the MGE can extend to 5.5 V vs. Li⁺/Li. The test cell using MGE as separator shows high initial discharge capacity (143 mAh g^-1 based on LiCoO₂) and high capacity retention ratio (around 94.8% at the 50th cycle). Generally, the special structural microporous membrane is promisingly used to prepare high-safety lithium-ion batteries.     

Generalized Poisson-Boltzmann Equation Taking into Account Ionic Interaction and Steric Effects

Generalized Poisson-Boltzmann equation which takes into account both ionic interaction in bulk solution and steric effects of adsorbed ions has been suggested.We found that,for inorganic cations adsorption on negatively charged surface,the steric effect is not significant for surface charge density 0.0032 Cdm 2,while the ionic interaction is an important effect for electrolyte concentration 0.15 moll in bulk solution.We conclude that for most actual cases the original PB equation can give reliable result in describing inorganic cation adsorption.     

Effect of monocationic ionic liquids as electrolyte additives on the electrochemical and thermal properties of Li-ion batteries

The conventional electrolyte system has been compared with the ionic liquid (IL) additive containing electrolyte system at room temperature as well as elevated temperature. In this work, two types of monocationic ILs such as 1-butyl-3-methylpyrrolidinium hexafluorophosphate (Pyr IL) and 1-ethyl-3-methylimidazolium hexafluorophosphate (IMI IL) are added as an additive at two different weight ratios in 1.15 M LiPF₆ (EC/EMC = 3/7 v/v) electrolyte solution, the structural, electrochemical and thermal characteristics of LiNi_0.80Co_0.15Al_0.05O₂ (NCA)/carbon full-cell in different electrolyte formulations have been reconnoitered. X-ray diffraction (XRD) studies have proved that IL as an electrolyte additive does not alter the structural stability of cathode materials after cycling. Under room temperature, Pyr IL additives at 1 wt% and 3 wt% deliver better cycleability than others, with the retention ratios of 93.62% and 92.8%, respectively. At elevated temperature, only 1 wt% Pyr IL additive is giving stable capacity retention ratio of 80.74%. Ionic conductivity and self-extinguishing time (SET) values are increasing with respect to the amount of additive added to the electrolyte. Thermal studies reveal that 3 wt% Pyr IL is favorable regarding the safety of the battery as it shows shifting of peak to higher temperature of 272.10 °C. Among the IL additives evaluated in this study, addition of 1 wt% Pyr IL is the most desirable additive for achieving the best cycling performance as well as thermal behavior of Li-ion batteries.     

Generalized Poisson-Boltzmann Equation Taking into Account Ionic Interaction and Steric Effects

Generalized Poisson-Boltzmann equation which takes into account both ionic interaction in bulk solution and steric effects of adsorbed ions has been suggested. We found that, for inorganic cations adsorption on negatively charged surface, the steric effect is not significant for surface charge density <0.0032 C/dm², while the ionic interaction is an important effect for electrolyte concentration >0.15 mol/l in bulk solution. We conclude that for most actual cases the original PB equation can give reliable result in describing inorganic cation adsorption.