电化学阻抗谱研究染料/Al2O3交替组装结构的光伏特性及作用机理

使用Al₂O₃和N3染料制备了一种交替组装的结构, 该结构能够提高染料敏化太阳能电池(DSCs)的开路电压(V_oc), 短路电流(J_sc)和转换效率(η). 为了研究(染料/Al₂O₃)交替组装结构的作用机理, 使用电化学阻抗谱技术分析了电池的界面电阻. 分析结果表明, 随着交替组装结构中(染料/Al₂O₃)单元的增加, 光阳极/染料/电解质界面的电阻降低, 电池性能随之提高. 基于电化学阻抗谱分析结果, 建立了一系列的等效电路模型, 从理论上解释了(染料/Al₂O₃)交替组装结构的作用机理.     

N3/Al2O3/N749交替组装结构拓宽准固态染料敏化太阳能电池光响应范围和界面修饰效果

研究了染料敏化太阳能电池(DSCs)中N3/Al₂O₃/N749交替组装结构的作用. 该结构使用Al₂O₃作为介质层吸附第二层染料, 可以有效拓宽DSCs的光响应范围, 提高电池的光电转化效率. UV-Vis 吸收光谱和单色光转换效率(IPCE)谱测试结果表明, 相对于单一染料, 使用交替组装结构的电池光响应范围变宽. 电流-电压(I-V)曲线结果表明, 该结构有效增加了DSCs 电池的光电转化效率, 从单一N3 和N749 染料的4.22%和3.09%增加到了5.75%, 分别增加了36%和86%. 为了研究该结构的作用机理, 本文对其界面修饰作用及界面电子过程进行了讨论. 暗电流测试结果表明交替组装结构可以有效阻止电荷复合过程; 电化学阻抗谱(EIS)结果表明在黑暗条件下, N3/Al₂O₃/N749结构可以提高界面电阻, 从而抑制电荷复合过程; 本文建立了等效电路模型, 并使用该模型讨论了交替组装结构的界面电子过程; 调制强度光电流谱(IMPS)和调制强度光电压谱(IMVS)的结果表明该结构可以提高电子寿命和改善电子扩散.     

Al2O3-CeO2复合电解质的制备及其半导体离子燃料电池性能

通过共沉淀法制备了Al₂O₃-CeO₂复合材料,并将其作为电解质应用于半导体离子燃料电池(SIFC)。探究了Al₂O₃、CeO₂物质的量之比不同的Al₂O₃-CeO₂复合电解质对SIFC电化学性能的影响。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对材料进行了表征。其中,Al₂O₃、CeO₂物质的量之比为1∶0.5的Al₂O₃-CeO₂ (1∶0.5)电池获得了最佳性能,在550 ℃下,开路电压为1.099 V时最大功率密度为1 142 mW·cm^-2。得益于复合电解质在测试气氛下两相间的界面效应,Al₂O₃-CeO₂ (1∶0.5)电池在较低测试温度下取得了优异的混合离子传导和功率输出性能。     

表面修饰的TiO2太阳能电池界面特性研究

用水热法制备了具有典型锐钛矿晶型的TiO₂纳米材料,采用Cr(NO₃)₃对TiO₂薄膜电极进行修饰改性。用X射线衍射(XRD)、扫描电子显微镜(SEM)和光电子能谱(XPS)测试电极的物相及表面结构,结果显示TiO₂薄膜表面包覆一层粒径较大的氧化铬颗粒,整个电极仍保持均匀的多孔结构。电流-电压(Ⅰ-Ⅴ)曲线测试结果显示,改性后最佳电极的短路电流和光电转换效率分别比改性前提高了31.1%和40.4%。用电化学阻抗谱(EIS)测试电池的界面特性,从测试结果可以看出,相同偏压下,改性后电池的TiO₂/染料/电解质界面电阻更大,说明氧化铬包覆层在一定程度上抑制了界面的电子复合,改善了电池的光电输出特性。     

Al2O3-CeO2复合电解质的制备及其半导体离子燃料电池性能

通过共沉淀法制备了Al₂O₃-CeO₂复合材料,并将其作为电解质应用于半导体离子燃料电池（SIFC）。探究了Al₂O₃、CeO₂物质的量之比不同的Al₂O₃-CeO₂复合电解质对SIFC电化学性能的影响。采用X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）对材料进行了表征。其中,Al₂O₃、CeO₂物质的量之比为1：0.5的Al₂O₃-CeO₂（1：0.5）电池获得了最佳性能,在550℃下,开路电压为1.099 V时最大功率密度为1 142 mW·cm^-2。得益于复合电解质在测试气氛下两相间的界面效应,Al₂O₃-CeO₂（1：0.5）电池在较低测试温度下取得了优异的混合离子传导和功率输出性能。     

Al掺杂对正极材料LiNi0.33-xMn0.33Co0.33AlxO2结构和电化学性能的影响

以柠檬酸为螯合剂利用快速湿化学法合成了具有α-NaFeO₂型层状结构的LiNi_0.33-xMn_0.33Co_0.33Al_xO₂(x=0.00,0.01,0.02, 0.04)正极材料,并通过X-射线衍射、充放电测试、循环伏安和交流阻抗对材料的结构和电化学性能进行了系统研究。XRD结果表明此方法合成的材料具有很好的层状结构且阳离子的混排度随着Al³⁺含量的增加而下降。电化学测试表明,LiNi_0.31Mn_0.33Co_0.33Al_0.02O₂具有很好的电化学性能和和循环性能,1C放电倍率下首次放电比容量达到176.9 mAh·g^-1,且Al³⁺的掺杂能有效提高电荷在电极界面间转移并抑制了在高压循环过程中电荷转移阻抗的增加。     

钠离子电池正极材料NaNi1/3Co1/3Mn1/3O2高压衰减机理

首次通过简单的固相反应合成了NaNi_1/3Co_1/3Mn_1/3O₂材料,并对其合适的电化学工作条件进行了探索。在此基础上对其在高充电电压下的衰减机理进行了研究。通过非原位XRD和电化学阻抗谱等电化学手段综合分析高充电电压下的衰减机理,发现随着充电电压升高至4 V,界面层的不断增厚与材料结构的不可逆变化同时导致了电化学性能的衰减。     

(ZrO2)0.86(Sm2O3)0.14纳米粉体的水热法合成及其烧结体的电性能

以湿化学法制得Zr(OH)₄和Sm(OH)₃的共沉淀为前驱体, 在碱性介质中用水热法合成了(ZrO₂)_0.86(Sm₂O₃)_0.14及(ZrO₂)_0.88(Sm₂O₃)_0.12纳米粉体. 将纳米粉体在较低温度(1450 ℃)下烧结制得了致密的固体电解质陶瓷样品, 比通常高温固相反应法采用的烧结温度(＞1600 ℃)降低了150 ℃以上. XRD测定结果表明, (ZrO₂)_0.86(Sm₂O₃)_0.14纳米粉体及其烧结体均为立方相, 但(ZrO₂)_0.88(Sm₂O₃)_0.12纳米粉体为立方相, 它的烧结体为立方相和单斜相的混合相. 用交流阻抗谱法、氧浓差电池法及氧泵(氧的电化学透过)法研究了(ZrO₂)_0.86(Sm₂O₃)_0.14陶瓷样品在600～1000 ℃下的离子导电特性. 结果表明, 该陶瓷样品在600～1000 ℃下氧离子迁移数为1, 氧离子电导率的最大值为3.2×10^－2 S•cm^－1, 是一个优良的氧离子导体; 它的氧泵性能明显地优于YSZ.     

钠离子电池正极材料NaNi1/3Co1/3Mn1/3O2高压衰减机理

首次通过简单的固相反应合成了NaNi_1/3Co_1/3Mn_1/3O₂材料,并对其合适的电化学工作条件进行了探索。在此基础上对其在高充电电压下的衰减机理进行了研究。通过非原位XRD分析结构的变化,同时结合电化学阻抗谱等电化学手段综合分析材料在高压下的充放机理。     

反相微乳液法制备纳米Al2O3颗粒及其形成反应机理的研究

通过聚乙二醇辛基苯基醚(曲拉通X-100)/正丁醇/环己烷/水溶液形成的体系, 采用反相微乳液法合成了Al₂O₃纳米粒子. 对前驱体进行热分析(TG-DTG-DTA), 确定了合适的煅烧温度为1150 ℃. 采用X射线衍射(XRD)、透射电镜(TEM)、紫外可见分光光度法(UV-vis)分别对产物的结构、粒度和形貌进行了表征, 考察了微乳液中水与表面活性剂的物质的量之比(ω_o)、煅烧温度和煅烧时升温速率等关键因素对产物形貌和晶相的影响, 并通过分析进一步揭示了Al₂O₃纳米粒子的形成机理. 结果表明, 控制ω_o为10、煅烧温度为1150 ℃可得到分散性好、粒径分布均匀的Al₂O₃纳米粒子, 且2 ℃/min的升温速率更有利于产物向稳定的α晶相转变.     

长链双烷基次膦酸作为共吸附剂修饰TiO_2光阳极

对TiO2/染料/电解质界面进行修饰是提高染料敏化太阳电池(DSC)性能的有效手段,其中引入共吸附剂有机小分子和染料共同吸附在TiO2表面是一种简单有效提高DSC性能的方法.本文合成了长链的双正十二烷基次膦酸(DDdPA)作为染料的共吸附剂应用于染料敏化太阳电池.通过红外光谱(FT-IR)表征DDdPA在TiO2表面的吸附;借助电化学阻抗谱(EIS)及强度调制光电流谱(IMPS)/强度调制光电压谱(IMVS)等技术表征了电子的传输与复合动力学过程.研究发现,DDdPA可以很好地与染料共同吸附在TiO2表面;与二(3,3-二甲基丁基)次膦酸(DINHOP)相比,DDdPA的引入可以更好地抑制TiO2/染料/电解质界面处的电子复合;在优化浓度配比下,DDdPA的引入有效提高了器件的电子寿命,使TiO2导带边负移约30 mV,最终使器件的开路电压提高了47 mV,光电转换效率提升约10%.     

Preparation, morphology and properties of nano-sized Al2O3/polyimide hybrid films

Nano-sized Al₂O₃/polyimide (PI) hybrid films based on 4,4′-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) were prepared by incorporation with different content of nano-sized Al₂O₃ via in situ polymerization. The TEM and SEM micrographs indicated that the Al₂O₃ particles were homogenously dispersed in the polyimide matrix by means of the ultrasonic treatment and the addition of coupling agent. The mechanical properties and thermal stability of the pure PI film can be improved by adequate addition of Al₂O₃. The PI hybrid film was strengthened and toughened simultaneously by the introduction of the well-dispersed Al₂O₃ particles. The PI hybrid films showed improved electrical aging performance as compared with pure PI film. Especially, the PI hybrid films with 10 wt.% of Al₂O₃ content exhibited obviously enhanced electrical aging performance with the time to failure of 3.4 times longer than that of pure PI film. The improved electrical aging performance of the hybrid film was attributed to the nano-sized Al₂O₃ particles highly dispersed in the hybrid film, which confirmed by the investigation of the morphology and the surface composition of PI hybrid film before and after electrical aging.     

TPR studies on steam reforming of 2-propanol on Rh/Al2O3, Ru/Al2O3 and Pd/Al2O3

Reaction pathways for steam reforming of 2-propanol (isopropyl alcohol, IPA) on Rh/Al₂O₃, Ru/Al₂O₃ and Pd/Al₂O₃ have been studied by temperature-programmed reactions (TPRs) of IPA and acetone in the presence of steam. The results of TPRs suggest that that of IPA on Rh/Al₂O₃ and Ru/Al₂O₃ proceeds via acetone, while the steam reforming of IPA on Pd/Al₂O₃ takes place via propene from acetone. This revised version was published online in August 2006 with corrections to the Cover Date.     

Influence of support on resistance to carbon-deposition of catalyst for CH4, CO2 with O2 to synthesis gas

In the reaction of catalytic oxidation of CH₄, CO₂ with O₂ to synthesis gas, carbon-deposition is an important factor for deactivation. By adding different oxides to Ni/Al₂O₃ catalyst, its resistance to carbon-deposition was improved. The experimental results indicate that the order of resistance to carbon-deposition is as follows: Ni/CaO-Al₂O₃>Ni/MgO-Al₂O₃>Ni/ TiO₂-Al₂O₃ > Ni/CeO₂-Al₂O₃>Ni/La₂O₃-Al₂O₃>Ni/Y₂O₃-Al₂O₃>Ni/Fe₂O₃-Al₂O₃>Ni/Al₂O₃. The catalysts were characterized by CO₂-TPD, O₂-TPD and XPS methods. Here the relation between the order of resistance to carbon-deposition and performance of catalyst is discussed.     

Li4Ti5O12/(Cu+C)复合材料的制备及电化学性能

以Li₄Ti₅O₁₂,Cu(CH₃COO)₂·H₂O和C₆H₁₂O₆为前驱体,化学沉积与热分解结合合成锂离子电池负极材料Li₄Ti₅O₁₂/(Cu+C)。采用X-射线衍射(XRD)、扫描电子显微镜(SEM)、恒流充放电、循环伏安和电化学阻抗方法表征样品的结构、形貌和电化学性能。结果表明,Li₄Ti₅O₁₂表面包覆的Cu与C提高了Li₄Ti₅O₁₂电极材料的导电率,其循环性能和倍率性能得到有效地改善。在0.5C、1C和3C倍率下,经过50次充放电循环,放电比容量分别为168.2、160、140.6 mAh·g^-1,其容量保持率分别为88.7%、84.4%、71.2%。电化学阻抗测试表明,表面包覆的Cu与C使其电荷转移阻抗大幅度减少。     

Influence of Pd-Ce interaction and chlorine ion on hydrodesulfurization reaction: The activity and sulfur tolerance of the Pd-Ceo2/Al2O3 catalyst

CeO₂ promoted palladium catalysts supported on Al₂O₃ were prepared using the impregnation (IM) and the deposition-precipitation (DP) methods. The activities and sulfur tolerance of the catalysts for hydrodesulfurization (HDS) were detected with thiophene HDS as probe reaction. H₂ adsorption, XRD, FTIR, NH₃-TPD, XPS were used to characterize the catalysts. The Pd-CeO₂/Al₂O₃ (IM) catalyst was highly active for the HDS reaction, and it had much stronger sulfur tolerance than the Pd/Al₂O₃ catalyst. Pd-CeO₂/Al₂O₃ (DP) showed excellent sulfur tolerance while its initial activity decreased. It was observed that with the chlorine bridge, the interfacial structure of Pd-Cl⁻¹-Ce³⁺ was responsible for the high activity of the Pd-CeO₂/Al₂O₃ (IM) catalyst, at the same time the interaction of Pd with Ce was weakened by Cl₋₁ ions. The enhanced sulfur tolerance over the Pd-CeO₂/Al₂O₃ (IM) catalyst was attributed to the weakened Pd-S bond caused by the competitive adsorption of H₂S on Ce³⁺ ions. As to the Pd-CeO₂/Al₂O₃ (DP) catalyst, a strong interaction of Pd with Ce put Pd at an electron-deficient state, the creation of sulfided palladium was therefore inhibited.     

过渡金属修饰Fe2O3/Al2O3氧载体的Redox性能研究

采用冷冻干燥法分别制备了经Cu、Co、Mn、Ni修饰的Fe₂O₃/Al₂O₃氧载体。利用化学吸附仪,通过程序升温还原(H₂-TPR)和程序升温氧化(TPO)来研究经不同过渡金属修饰的Fe₂O₃/Al₂O₃与H₂和O₂的反应性能。实验发现,在Fe₂O₃/Al₂O₃中加入Cu、Co、Ni以后,氧载体与H₂的反应性都有提高,但是当在Fe₂O₃/Al₂O₃中加入Mn以后,氧载体的反应性和载氧能力反而下降。经Cu修饰的Fe₂O₃/Al₂O₃与H₂的反应性最高,且具有很好的反应稳定性,适合用于化学链燃烧。     

Selective Catalytic Reduction of NO with Propene over Au/Fe2O3/Al2O3 Catalysts

A series of Au/Fe₂O₃/Al₂O₃ catalysts were prepared by the homogeneous deposition-precipitation method. The catalytic activity of the catalyst samples for selective catalytic reduction of NO by propene under oxygen-rich atmosphere was evaluated. The results showed that 2%Au/10%Fe₂O₃/Al₂O₃ exhibited good low-temperature activity. The maximum of NO conversion reached 43% at 300 °C, while it was only 21% over the 2%Au/Al₂O₃ catalyst at the same temperature. The addition of 2% steam to the feed gas had little effect on the catalytic activity. X-ray diffraction results indicated that both Au and Fe₂O₃ particles were highly dispersed over Al₂O₃. H₂-temperature-programmed reduction results indicated that there was strong interaction between Au and Fe₂O₃, which made the reduction of Fe₂O₃ easy. The synergistic effect between Au and Fe₂O₃ was probably responsible for the good catalytic performance of the Au/Fe₂O₃/Al₂O₃ catalyst at low temperature.