纳米TiO2多孔薄膜电极平带电势的研究

采用光谱电化学方法研究了纳米TiO₂多孔薄膜电极的平带电势,获得了薄膜厚度以及TiCl₄处理对纳米TiO₂薄膜电极平带电势的影响情况,并研究了平带电势对染料敏化太阳电池光伏性能的影响.结果表明,可以通过检测纳米TiO₂电极平带电势的变化趋势来反映电池中TiO₂电极平带电势的变化趋势.随着TiO₂电极膜厚的增加,其平带电势将向正方向移动,导致对应电池的开路电压随之减小.另外,经 关键词： 平带电势 2')" href="#">纳米TiO₂ 染料敏化 太阳电池     

大面积染料敏化太阳电池的串联阻抗特性研究

在电子扩散微分方程的基础上,研究了染料敏化太阳电池光生电流和光生电压随光照强度不同的变化关系.提出敏化太阳电池串联阻抗功率损耗模型,理论模拟了大面积电池（有效面积>1 cm²）光电转换效率随多孔薄膜有效面积宽度变化的曲线、透明导电基底膜与银栅极的比接触电阻以及在不同入射光强下银栅极体电阻对大面积染料敏化太阳电池光伏性能的影响.结果表明透明导电基底膜的方块电阻和银栅极体电阻对大面积染料敏化太阳电池的性能有很大影响,而这种影响随光强的减弱逐渐减小. 关键词： 染料敏化 太阳电池 串联阻抗 光电转换效率     

染料敏化太阳电池中TiO2膜内电子传输和背反应特性研究

采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)研究电池内部电子传输机理和电子背反应动力学特性.利用理论表达式对不同TiO₂多孔膜厚度(d)的电池实验数据进行了拟合,得到了电池的吸收系数(α)、电子扩散系数(D_n)、电子寿命(τ_n)、电子传输时间(τ_d)和入射单色光光电转化效率(IPCE)等微观参数的数值.研究表明：膜薄有利于加快电子传 关键词： 染料敏化 太阳电池 IMPS/IMVS 传输     

锐钛矿相TiO2纳米管的制备及其染料敏化太阳电池

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的方法合成TiO₂纳米管.采用SEM,TEM,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 关键词： 2纳米管')" href="#">TiO₂纳米管 染料敏化太阳电池 水热法     

电沉积处理与染料敏化纳米薄膜太阳电池的优化

采用阳极氧化水解法对染料敏化纳米TiO₂薄膜太阳电池的光阳极进行不同方式的电沉积优化处理.借助x射线衍射仪对处理后的样品进行分析，通过超高分辨率场发射扫描电子显微镜对导电玻璃以及电沉积处理前后纳米多孔薄膜表面进行了粒径和形貌的扫描.染料敏化太阳电池实验测试结果表明，电沉积处理和修饰后可以明显提高光生电子的收集率，增大短路电流密度，提高电池效率. 关键词： 2')" href="#">纳米TiO₂ 染料敏化 电沉积 太阳电池     

电极表面改性对染料敏化太阳电池性能影响的机理研究

采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术,从染料敏化太阳电池(DSC)电子传输和复合角度对比了不同光强下导电玻璃表面阻挡层及TiO₂薄膜优化使电池性能改善的内在原因.阻挡层的引入和TiO₂薄膜的优化均通过电沉积法实现.结果表明,对多孔薄膜电极的不同改性均提高了电池的短路电流J_sc和效率η,但对电子传输和复合过程的作用机理有所不同:前者延长了电子寿命τ _n,但电子传输时间τ _d变化不明显;而后者则主要是延长τ _n的同时也缩短了τ _d. 关键词： 染料敏化 太阳电池 调制光电流谱/调制光电压谱 电子输运     

纳米TiO2颗粒/亚微米球多层结构薄膜内电荷传输性能研究

本文主要利用TiO₂亚微米球较强的光散射特性设计了纳米TiO₂颗粒/亚微米球多层结构光阳极, 并借助强度调制光电流谱(intensity-modulated photocurrent spectroscopy)、电化学阻抗谱(electrochemical impedance spectroscopy)和入射单色光光电转化效率(incident photon-to-current conversion efficiency), 研究亚微米球的引入对多层结构薄膜内缺陷态、电子传输时间、电子收集效率和界面电荷转移性能的影响. 强度调制光电流谱反映出亚微米球表面缺陷态少, 但其颗粒间接触不紧密, 导致在接触部位形成了势垒, 阻碍了电子的传输, 导致电子传输时间增长. 电化学阻抗谱结果表明不同多层结构电池界面复合无明显差别, 同时底层采用纳米TiO₂ 透明薄膜结构的电池, 其光利用率要明显高于底层采用亚微米球薄膜结构的电池, TiO₂费米能级电子填充水平也相对增大, 使得电池的光电转换效率得到提升. 多层结构复合薄膜电荷传输和光伏特性的研究, 为高效染料敏化太阳电池光阳极设计提供了实验基础.     

聚苯胺基固态染料敏化太阳电池中电子输运性能的研究

以导电聚苯胺为空穴传输材料，制备了固态染料敏化太阳电池(DSC).利用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)研究了TiO₂多孔膜内的电子输运及复合过程.通过TiO₂多孔膜内电子的平均传输时间(τ_d)和电子寿命(τ_n)及对IMPS实验数据的拟合，获得电子在TiO₂膜内的有效扩散系数(D_n)和扩散长度(L_n).这些聚苯胺基电池中的τ_n值为相应的液体型电池的1/10倍左右，表明在该固体电池中存在严重的光生电子的复合过程，这很可能主要是与氧化态染料分子和导电电子间的复合有关.随着TiO₂膜厚的增加，τ_n和τ_d均变小，但D_n和L_n随之增加，只有在合适的膜厚范围内才能获得较高的光伏性能. 关键词： 聚苯胺 染料敏化太阳电池 IMPS IMVS     

TiCl4处理多孔薄膜对染料敏化太阳电池中电子传输特性影响研究

借助于强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术,研究了纳米TiO₂多孔薄膜在TiCl₄溶液处理后组装成的染料敏化太阳电池(DSC)中电子传输和背反应动力学特性. 研究表明:纳米TiO₂多孔薄膜经TiCl₄溶液处理后,电池中暗电流减小,电子寿命τ_n明显延长,电子传输时间τ_d缩短,电子有效扩散系数D_n增大,电子扩散长度L_n值升高,入射单色光子/电子转化效率η_IPCE增加,光生电荷量Q_oc显著增加. 文章从微观层面上研究了TiCl₄溶液处理纳米TiO₂多孔薄膜对DSC内部电子的产生、传输和复合过程的影响,从而很好地解释了电池光伏性能随TiCl₄溶液处理的变化关系. 关键词： 4')" href="#">TiCl₄ 电子传输 染料敏化 太阳电池     

染料敏化太阳电池中TiO2颗粒界面接触对电子输运影响的研究

采用溶胶-凝胶法制备TiO₂浆料,通过丝网印刷技术印刷和不同温度曲线烧结TiO₂薄膜,并应用于染料敏化太阳电池(DSC).高分辨透射电子显微镜发现,低温下多孔薄膜中TiO₂颗粒之间呈现点接触,510 ℃烧结后TiO₂颗粒间由点接触变为面接触,近邻颗粒数增多,接触面积增大.同时采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术,研究了不同颗粒接触方式和接触面积对电子传输与复合的影响.结果表明:在420- 510 ℃之间,随着烧结温度提高,颗粒接触面积增大,电子传输时间(τ _d)缩短,电子有效扩散长度(L _n)增大,暗电流减小;当烧结温度达到550 ℃时,薄膜比表面积减小,多孔结构坍塌,表面态密度增大,电子传输时间(τ _d)增大.电池光伏特性研究表明:在480-510 ℃范围内烧结得到的TiO₂薄膜,电池短路电流密度(J_sc)最佳,电池效率(η)最好. 关键词： 界面接触 电子输运 暗电流 染料敏化太阳电池     

Electrochemical properties of thin TiO2 electrode on Li1 + xAlxGe2 − x(PO4)3 solid electrolyte

A fabrication of all-solid-state thin-film rechargeable lithium ion batteries by sol-gel method is expected to achieve both the simplification and cost reduction for fabrication process. TiO₂ thin film electrode was prepared by PVP (polyvinylpyrrolidone) sol-gel method combined with spin-coating on Li_1 + xAl_xGe_2 − x(PO₄)₃ (LAGP) solid electrolyte which has wide electrochemical window. The thin film was composed of anatase TiO₂ that is the most active phase for Li insertion and extraction and contacted well with LAGP substrate. In the cyclic voltammogram, a redox couple was observed at 1.8 V vs. Li/Li⁺ assigned to Li insertion/extraction into/from anatase TiO₂, indicating that the thin film worked as electrode for lithium battery. The charge and discharge test in various charge and discharge rates revealed that the discharge process (delithiation) is thought to be faster than charge process (lithiation). It is attested that the sol-gel process, which derives both simplification and cost reduction for fabrication process, can be applied to thin film battery using LAGP solid electrolyte.     

A lithium salt additive Li<Subscript>2</Subscript>ZrF<Subscript>6</Subscript> for enhancing the electrochemical performance of high-voltage LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode

In this work, Li₂ZrF₆, a lithium salt additive, is reported to improve the interface stability of LiNi_0.5Mn_1.5O₄ (LNMO)/electrolyte interface under high voltage (4.9 V vs Li/Li⁺). Li₂ZrF₆ is an effective additive to serve as an in situ surface coating material for high-voltage LNMO half cells. A protective SEI layer is formed on the electrode surface due to the involvement of Li₂ZrF₆ during the formation of SEI layer. Charge/discharge tests show that 0.15 mol L^?1 Li₂ZrF₆ is the optimal concentration for the LiNi_0.5Mn_1.5O₄ electrode and it can improve the cycling performance and rate property of LNMO/Li half cells. The results obtained by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) demonstrate that Li₂ZrF₆ can facilitate the formation of a thin, uniform, and stable solid electrolyte interface (SEI) layer. This layer inhibits the oxidation decomposition of the electrolyte and suppresses the dissolution of the cathode materials, resulting in improved electrochemical performances.     

Effect of substrate bias voltage on the structure, electric and dielectric properties of TiO2 thin films by DC magnetron sputtering

Titanium dioxide (TiO₂) films have been deposited on glass and p-silicon (1 0 0) substrates by DC magnetron sputtering technique to investigate their structural, electrical and optical properties. The surface composition of the TiO₂ films has been analyzed by X-ray photoelectron spectroscopy. The TiO₂ films formed on unbiased substrates were amorphous. Application of negative bias voltage to the substrate transformed the amorphous TiO₂ into polycrystalline as confirmed by Raman spectroscopic studies. Thin film capacitors with configuration of Al/TiO₂/p-Si have been fabricated. The leakage current density of unbiased films was 1 × 10⁻⁶ A/cm² at a gate bias voltage of 1.5 V and it was decreased to 1.41 × 10⁻⁷ A/cm² with the increase of substrate bias voltage to −150 V owing to the increase in thickness of interfacial layer of SiO₂. Dielectric properties and AC electrical conductivity of the films were studied at various frequencies for unbiased and biased at −150 V. The capacitance at 1 MHz for unbiased films was 2.42 × 10⁻¹⁰ F and it increased to 5.8 × 10⁻¹⁰ F in the films formed at substrate bias voltage of −150 V. Dielectric constant of TiO₂ films were calculated from capacitance–voltage measurements at 1 MHz frequency. The dielectric constant of unbiased films was 6.2 while those formed at −150 V it increased to 19. The optical band gap of the films decreased from 3.50 to 3.42 eV with the increase of substrate bias voltage from 0 to −150 V.     

Titanium-modified Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> with a synergistic effect of surface modifying,bulk doping,and size reducing

In this work, a one-step solid-phase sintering process via TiO₂ and Li₂CO₃ under an argon atmosphere, with ultra-fine titanium powder as the modifying agent, was used to prepare a nano-sized Li₄Ti₅O₁₂/Ti composite (denoted as LTO–Ti) at 800 °C. The introduction of ultra-fine metal titanium powder played an important role. First, X-ray photoelectron spectroscopy demonstrates that Ti⁴⁺ was partially changed into Ti³⁺, through the reduction of the ultra-fine metal titanium powder. Second, X-ray diffraction revealed that the ultra-fine metal titanium powder did not react with the bulk structure of Li₄Ti₅O₁₂, while some pure titanium peaks could be seen. Additionally, the size of LTO–Ti particles could be significantly reduced from micro-scale to nano-scale. The structure and morphology of LTO–Ti were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. Electrochemical tests showed a charge/discharge current of 0.5, 1, 5, and 10 C; the discharge capacity of the LTO–Ti electrode was 170, 161, 140, and 111 mAh g^?1. It is believed that the designed LTO–Ti composite makes full use of both components, thus offering a large contact area between the electrolyte and electrode, high electrical conductivity, and lithium-ion diffusion coefficient during electrochemical processes. Furthermore, ultra-fine titanium powder, as the modifying agent, is amenable to large-scale production.     

Enhanced electrical properties of polyethylene oxide (PEO) + polyvinylpyrrolidone (PVP):Li<Superscript>+</Superscript> blended polymer electrolyte films with addition of Ag nanofiller

Polymer blended films of polyethylene oxide (PEO)?+?polyvinyl pyrrolidone (PVP):lithium perchlorate (LiClO₄) embedded with silver (Ag) nanofiller in different concentrations have been synthesized by a solution casting method. The semi-crystalline nature of these polymer films has been confirmed from their X-ray diffraction (XRD) profiles. Fourier transform infrared spectroscopy (FTIR) and Raman analysis confirmed the complex formation of the polymer with dopant ions. Dispersed Ag nanofiller size evaluation study has been done using transmission electron microscopy (TEM) analysis. It was observed that the conductivity increases when increasing the Ag nanofiller concentration. On the addition of Ag nanofiller to the polyethylene oxide (PEO)?+?polyvinyl pyrrolidone (PVP):Li⁺ electrolyte system, it was found to result in the enhancement of ionic conductivity. The maximum ionic conductivity has been set up to be 1.14?×?10^?5 S cm^?1 at the optimized concentration of 4 wt% Ag nanofiller-embedded (45 wt%) polyethylene oxide (PEO)?+?(45 wt%) polyvinyl pyrrolidone (PVP):(10 wt%) Li⁺ polymer electrolyte nanocomposite at room temperature. Polyethylene oxide (PEO)?+?polyvinyl pyrrolidone (PVP):Li⁺ +Ag nanofiller (4 wt%) cell exhibited better performance in terms of cell parameters. This is ascribed to the presence of flexible matrix and high ionic conductivity. The applicability of the present 4 wt% Ag nanofiller-dispersed polyethylene oxide (PEO)?+?polyvinyl pyrrolidone (PVP):Li⁺ polymer electrolyte system could be suggested as a potential candidate for solid-state battery applications. Dielectric constants and dielectric loss behaviours have been studied.     

Characterization of a LiCoO2 thin film cathode grown by pulsed laser deposition

A highly (003)-oriented pure LiCoO₂ thin film cathode, without Co₃O₄ impurities, was grown on a stainless steel substrate by pulsed laser deposition and characterized by electrochemical testing, scanning electron microscopy (SEM), ex situ X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS). The initial reversible discharge capacity of the LiCoO₂ thin film cathode reached 52.5?μAh/cm²µm and capacity loss was about 0.18% per cycle at a current density of 12.74?μA/cm². The chemical diffusion coefficient of the Li⁺ ion was estimated to be about 4.7?×?10^?11?cm²/s from cyclic voltammetric (CV) scans. Ex situ XRD revealed that the spacing of crystalline planes expanded about 0.09?Å when charged to 4.2?V, corresponding to Li_0.5CoO₂, lower than the value for composite powder LiCoO₂ electrodes. XPS results showed that the number of low-coordinated oxygen ions increased relative to the removal of Li⁺ ions.     

Crystalline-structure-dependent green and red upconversion emissions of Er-Yb-Li codoped TiO2

Crystalline structures and infrared-to-visible upconversion luminescence spectra have been investigated in 1 mol% Er³⁺, 10 mol% Yb³⁺ and 0-20 mol% Li⁺ codoped TiO₂ [1Er10Yb(0-20)Li:TiO₂] nanocrystals. The crystalline structures of 1Er10Yb(0-20)Li:TiO₂ were divided into three parts by the addition of Yb³⁺ and Li⁺. Both green and red upconversion emissions were observed from the ²H_11/2/⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ in Er³⁺-Yb³⁺-Li⁺ codoped TiO₂, respectively. The green and red upconversion emissions of 1Er:TiO₂ were enhanced significantly by Yb³⁺ and Li⁺ codoping, in which the intensities of green and red emissions and the intensity ratio of green to red emissions (I_green/I_red) were highly dependent on the crystalline structures. The significant enhanced upconversion emissions resulted from the energy migration between Er³⁺ and Yb³⁺ as well as the distortion of crystal field symmetry of Er³⁺ caused by the dissolving of Li⁺ at lower Li⁺ codoping concentration and the phase transformation at higher Li⁺ concentration. It is concluded that codoping with ions of smaller ionic radius like Li⁺ can efficiently improve the upconversion emissions of Er³⁺ or other rare-earth ions doped luminsecence materials.     

退火气压对Bi3.25La0.75Ti3O12铁电薄膜的微观结构和铁电性能的影响

采用sol-gel法在Pt/TiO₂/SiO₂/p-Si(100)衬底上制备了Bi_3.25La_0.75Ti₃O₁₂(BLT)铁电薄膜,研究了在750 ℃时不同退火气压(p_{O2:10^-4—3 atm)对薄膜微观结构和电学性能的影响.XRD和拉曼光谱结果表明在10^-4和3 atm氧气压下退火 关键词： 3.25}La_0.75Ti₃O₁₂')" href="#">Bi_3.25La_0.75Ti₃O₁₂ 铁电性能 sol-gel法 正交化度     

The roles of Li and F ions in Li-F-codoped TiO2 system

An overall comparative study was carried out on Li-doped, F-doped, and Li-F-codoped TiO₂ powders in order to elucidate the roles of Li⁺ and F⁻ ions in photocatalyst. The characteristic data were based on the analysis of XRD, XPS, and PL spectra. The effects of atomic ratio of Li/Ti and F/Ti on the photocatalytic activity were also investigated. As the results, Li doping accelerated the phase formation of rutile in lower temperature while F doping prevented the phase transition from anatase to rutile. Li doping inducted a large amount of O_OH on the surface of TiO₂, while F doping consumed much of O_OH. Li⁺ ions acted as the roles of recombination center of electron-hole pairs while F doping could restrain the recombination of electron-hole pairs on the center of Li⁺ ions. The roles of Li⁺ and F⁻ ions were also confirmed in the experimental section, where the photocatalytic activity of TiO₂ was improved greatly by synergistic reaction of Li⁺ and F⁻ ions.