Ti doping

  • 文章类型: Journal Article
    研究了钛(Ti)掺杂对二氧化钒(VO2)光学性能的影响,一种以接近室温的金属到绝缘体转变(MIT)而闻名的材料。通过将Ti掺入到VO2的晶格中,我们的目标是揭示其物理性质的变化,对于增强其在智能设备中的应用至关重要。利用偏振红外显微光谱,我们检查了从远红外到可见光谱范围的不同晶相(导电金红石相和绝缘单斜相M1和M2)中不同Ti浓度(x=0.059,x=0.082和x=0.187)的TixV1-xO2单晶。我们的发现表明,Ti掺杂显着影响声子光谱,引入不归因于纯VO2或TiO2的吸收峰。这在沿晶体生长轴的极化中尤其值得注意,主要在x=0.187样本中。此外,我们证明了电子对金属相中的光学电导率的贡献表现出强烈的各向异性,沿c轴高于a-b平面。这种各向异性,加上随着掺杂的增加,区域中心红外有源声子模式逐渐变宽,强调了掺杂VO2中结构动力学和电子动力学之间复杂的相互作用。我们的结果强调了Ti掺杂在微调VO2的电子和热致变色性能中的潜力,为其在光电设备和技术中的增强应用铺平了道路。
    This study delves into the effects of titanium (Ti) doping on the optical properties of vanadium dioxide (VO2), a material well known for its metal-to-insulator transition (MIT) near room temperature. By incorporating Ti into VO2\'s crystal lattice, we aim to uncover the resultant changes in its physical properties, crucial for enhancing its application in smart devices. Utilizing polarized infrared micro-spectroscopy, we examined TixV1-xO2 single crystals with varying Ti concentrations (x = 0.059, x = 0.082, and x = 0.187) across different crystal phases (the conductive rutile phase and insulating monoclinic phases M1 and M2) from the far-infrared to the visible spectral range. Our findings reveal that Ti doping significantly influences the phononic spectra, introducing absorption peaks not attributed to pure VO2 or TiO2. This is especially notable with polarization along the crystal growth axis, mainly in the x = 0.187 sample. Furthermore, we demonstrate that the electronic contribution to optical conductivity in the metallic phase exhibits strong anisotropy, higher along the c axis than the a-b plane. This anisotropy, coupled with the progressive broadening of the zone center infrared active phonon modes with increasing doping, highlights the complex interplay between structural and electronic dynamics in doped VO2. Our results underscore the potential of Ti doping in fine-tuning VO2\'s electronic and thermochromic properties, paving the way for its enhanced application in optoelectronic devices and technologies.
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  • 文章类型: Journal Article
    正极材料Na4Fe3(PO4)2P2O7(NFPP)由于其成本效益,在钠离子电池(SIB)中显示出巨大的潜力,延长循环寿命,高理论能力。然而,NFPP的实际大规模生产受到其差的固有电子传导性和NaFePO4杂质的存在的阻碍。在这项研究中,我们提出了一种涉及Ti掺杂的相辅相成的方法,机械纳米处理,和原位碳涂层,通过固态合成方法生产Ti-NFPP。Ti掺杂增强了共价Fe-O相互作用,从而加速电子转移和氧化还原反应Fe2+/Fe3+。原位碳涂层改善了导电性并允许适应体积变化。纳米级处理促进固态反应的均匀进展。合成的Na4Fe2.98Ti0.01(PO4)2P2O7材料(Ti-NFPP)表现出有希望的电化学性能,在0.1C下的初始放电比容量为112.5mAhg-1。在脱/皂化过程中观察到的体积变化仅为2.98%,表明晶格的可逆性增强。此外,它显示了优异的循环稳定性,在10℃下5000次循环的容量保持率为97.2mAhg-1。这些发现为在SIB中大规模生产Ti-NFPP提供了有希望的途径。
    The cathode material Na4Fe3(PO4)2P2O7 (NFPP) has shown great potential for sodium-ion batteries (SIBs) due to its cost-effectiveness, prolonged cycle life, and high theoretical capacity. However, the practical large-scale production of NFPP is hindered by its poor intrinsic electron conductivity and the presence of a NaFePO4 impurity. In this study, we propose a mutually reinforcing approach involving Ti doping, mechanical nano treatment, and in situ carbon coating to produce Ti-NFPP via the solid-state methods of synthesis. Ti doping strengthens the covalent Fe-O interaction, hence accelerating the electron transfer and the redox reactions Fe2+/Fe3+. In situ carbon coating improves electrical conductivity and allows for accommodating the volumetric variation. Nanosized treatment promotes the uniform progression of solid-state reactions. The synthesized Na4Fe2.98Ti0.01(PO4)2P2O7 material (Ti-NFPP) exhibits promising electrochemical properties with an initial discharge specific capacity of 112.5 mA h g-1 at 0.1 C. A volumetric change of only 2.98% was observed during the de/sodiation process, indicating an enhanced reversibility of the crystal lattice. Moreover, it demonstrates exceptional cycling stability with a capacity retention rate of 97.2 mA h g-1 at 10 C over 5000 cycles. These findings offer a promising pathway for the large-scale production of Ti-NFPP in SIBs.
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  • 文章类型: Journal Article
    采用第一性原理计算和实验分析,综合研究了Ti掺杂对无压浸渗SiCp/Al复合材料组织和性能的影响。第一性原理计算表明,Ti掺杂可以显着提高Al/SiC系统中的界面润湿和结合强度。随后,将Ti元素以TiO2和TiC的形式掺入SiC预制件中,以验证Ti掺杂对SiCp/Al复合材料无压浸渗性能的影响。实验结果表明,添加TiC或TiO2可改善润湿性,从而促进熔融Al无压渗入SiC预制件。然而,掺入TiO2导致AlN晶须在N2气氛下生长,从而阻碍了复合材料的完全致密化。另一方面,TiC掺杂可以改善润湿性和界面强度而没有有害反应。因此,TiC掺杂SiCp/Al复合材料表现出优异的性能,包括99.4%的高相对密度,弯曲强度为287±18MPa,热导率为142W·m-1·K-1。
    The effects of Ti doping on the microstructure and properties of SiCp/Al composites fabricated by pressureless infiltration were comprehensively investigated using first-principles calculations and experimental analyses. First-principles calculations revealed that the interface wetting and bonding strength in an Al/SiC system could be significantly enhanced by Ti doping. Subsequently, the Ti element was incorporated into SiC preforms in the form of TiO2 and TiC to verify the influence of Ti doping on the pressureless infiltration performance of SiCp/Al composites. The experimental results demonstrated that the pressureless infiltration of molten Al into SiC preforms was promoted by adding TiC or TiO2 due to the improved wettability. However, incorporating TiO2 leads to the growth of AlN whiskers under a N2 atmosphere, thereby hindering the complete densification of the composites. On the other hand, TiC doping can improve wettability and interface strength without deleterious reactions. As a consequence, the TiC-doped SiCp/Al composites exhibited excellent properties, including a high relative density of 99.4%, a bending strength of 287 ± 18 MPa, and a thermal conductivity of 142 W·m-1·K-1.
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  • 文章类型: Journal Article
    层状Na2FePO4F(NFPF)正极材料因其绿色无毒性而受到广泛关注,丰富的原材料,和低成本。然而,其固有的导电性差和缓慢的钠离子传输严重阻碍了其容量输送和循环稳定性。在这项工作中,NFPF由Ti搀杂和共形碳层包覆经由固相反响改性。实验研究和密度泛函理论计算结果表明,Ti掺杂提高了本征电导率,加速钠离子的传输,并产生更多的钠离子储存位点,和来自聚乙烯吡咯烷酮(PVP)的热解碳均匀地涂覆在NFPF表面上,改善了表面/界面导电性并抑制了副反应。在Ti掺杂和碳涂层的共同作用下,优化的NFPF(标记为5T-NF@C)表现出优异的电化学性能,在0.2C时具有108.4mAhg-1的高容量,即使在10C的高电流密度下,也有80.0mAhg-1的可观容量,在10C下2000次循环后的高容量保持率为81.8%。当组装成带有硬碳阳极的全电池时,5T-NF@C也表示出较好的适用性。这项工作表明,Ti掺杂和碳涂层的共改性使NFPF实现了钠离子电池的高倍率和长循环性能。
    Layered Na2FePO4F (NFPF) cathode material has received widespread attention due to its green nontoxicity, abundant raw materials, and low cost. However, its poor inherent electronic conductivity and sluggish sodium ion transportation seriously impede its capacity delivery and cycling stability. In this work, NFPF by Ti doping and conformal carbon layer coating via solid-state reaction is modified. The results of experimental study and density functional theory calculations reveal that Ti doping enhances intrinsic conductivity, accelerates Na-ion transport, and generates more Na-ion storage sites, and pyrolytic carbon from polyvinylpyrrolidone (PVP) uniformly coated on the NFPF surface improves the surface/interface conductivity and suppresses the side reactions. Under the combined effect of Ti doping and carbon coating, the optimized NFPF (marked as 5T-NF@C) exhibits excellent electrochemical performance, with a high capacity of 108.4 mAh g-1 at 0.2C, a considerable capacity of 80.0 mAh g-1 even at high current density of 10C, and a high capacity retention rate of 81.8% after 2000 cycles at 10C. When assembled into a full cell with a hard carbon anode, 5T-NF@C also show good applicability. This work indicates that co-modification of Ti doping and carbon coating makes NFPF achieve high rate and long cycle performance for sodium-ion batteries.
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  • 文章类型: Journal Article
    Yb0.4Co4Sb12,是一个经过充分研究的系统,由于Yb填料原子驱动的大电荷载流子浓度和较低的热导率值,因此显示出明显的高电性能。在这项工作中,YbzCo4-xTixSb12(其中z=0,x=0和z=0.4,x=0,0.04和0.08)在300-700K的温度范围内研究了通过熔融淬火退火然后进行放电等离子烧结(SPS)制备的Ti掺杂的热电性能。在300K时,Yb的添加和施主Ti的掺杂同时将电导率提高到1453.5S/cm,最终将Yb0.4Co3.96Ti0.04Sb12中的功率因数提高到675K时的〜4.3mW/(m·K2)。相反,热导率的显着降低从〜7.69W/(m·K)(Co4Sb12)到〜3.50W/(m·K)(Yb0.4Co3.96Ti0.04Sb12)在〜300K。对于Yb0.4Co3.96Ti0.04Sb12的组成,最大zT在623K时达到〜0.85,高硬度为584HV,这表明它是适用于中温热电应用的有效材料。
    Yb0.4Co4Sb12, being a well-studied system, has shown notably high thermoelectric performance due to the Yb filler atom-driven large concentration of charge carriers and lower value of thermal conductivity. In this work, the thermoelectric performance of YbzCo4-xTixSb12 (where z = 0, x = 0 and z = 0.4, x = 0, 0.04, and 0.08) upon Ti doping prepared by the melt-quenched-annealing followed by spark plasma sintering (SPS) has been studied in the temperature range of 300-700 K. Addition of Yb and doping of donor Ti at the Co site simultaneously increase the electrical conductivity to 1453.5 S/cm at 300 K, which ultimately boosts the power factor as high as ∼4.3 mW/(m·K2) at 675 K in Yb0.4Co3.96Ti0.04Sb12. Adversely, a significant reduction in thermal conductivity is obtained from ∼7.69 W/(m·K) (Co4Sb12) to ∼3.50 W/(m·K) (Yb0.4Co3.96Ti0.04Sb12) at ∼300 K. As a result, the maximum zT is achieved as ∼0.85 at 623 K with high hardness of 584 HV for the composition of Yb0.4Co3.96Ti0.04Sb12, which demonstrates it to be an efficient material suitable for intermediate temperature thermoelectric applications.
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  • 文章类型: Journal Article
    在这项研究中,采用化学溶液分解法制备了不同成分的Ti掺杂Bi2O3光催化材料。用于降解活性亮蓝KN-R,然后用XRD表征,SEM,UV-visDRS,XPS,光电流,和其他检测方法。结果表明,当催化剂用量为1.0g/L,活性艳蓝KN-R的初始浓度为20mg/L时,纯Bi2O3对活性艳蓝KN-R的降解率为75.30%;Ti掺杂量为4%(4Ti/Bi2O3),4Ti/Bi2O3对活性艳蓝KN-R的降解效果最好,降解率可达93.27%。当4Ti/Bi2O3重复使用4次时,活性艳蓝KN-R的降解率仅降低了6.91%。掺杂Ti可以抑制Bi2O3晶粒的生长,使Ti/Bi2O3材料的XRD峰变宽。纯Bi2O3颗粒较大且表面光滑。随着Ti掺杂量的增加,Ti/Bi2O3材料的表面从粗糙生长到纳米纤维Bi4Ti3O12。掺杂Ti离子显著提高了Bi2O3的可见光吸收性能和电子分离转移能力。带隙从2.81eV减小到2.75eV。总之,Ti掺杂增强了Bi2O3的可见光吸收和电子分离转移能力,并改善了表面形貌,这使得Bi2O3具有更高的光催化性能。
    In this study, different compositions of Ti-doped Bi2O3 photocatalytic materials were prepared by chemical solution decomposition method. It was used to degrade reactive brilliant blue KN-R, and then characterized by XRD, SEM, UV-vis DRS, XPS, photocurrent, and other detection methods. The results show that when the catalyst dosage is 1.0 g/L and the initial concentration of reactive brilliant blue KN-R is 20 mg/L, the degradation rate of pure Bi2O3 to reactive brilliant blue KN-R is 75.30%; the Ti doping amount is 4% (4Ti/Bi2O3), 4Ti/Bi2O3 had the best degradation effect on reactive brilliant blue KN-R, and the degradation rate could reach 93.27%. When 4Ti/Bi2O3 was reused for 4 times, the degradation rate of reactive brilliant blue KN-R only decreased by 6.91%. Doping Ti can inhibit the growth of Bi2O3 grains, making the XRD peak of Ti/Bi2O3 material wider. The pure Bi2O3 particles are larger and the surface is smooth. With the increase of Ti doping content, the surface of Ti/Bi2O3 material grows from roughness to nanofibrous Bi4Ti3O12. The visible light absorption performance and electron separation and transfer ability of Bi2O3 are significantly improved by doping Ti ions. The band gap is reduced from 2.81 to 2.75 eV. In conclusion, doping Ti enhances the visible light absorption and electron separation and transfer capabilities of Bi2O3, reduces the band gap, and improves the surface morphology, which makes Bi2O3 have higher photocatalytic performance.
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  • 文章类型: Journal Article
    我们提出了一种钛掺杂和表面涂覆富Mn壳的协同策略,以修饰钠离子电池中富Na锰氧化物基阴极材料Na0.67Ni0.33Mn0.67-xTixO1.9F0.1,并阐明了增强材料性能的潜在机理。首先,发现当Ti掺杂量为x=0.3时,可以有效改善正极材料的电化学性能。除了掺杂,通过液体涂覆法制备了涂覆有富锰壳的正极材料。制备的Mn@Ti掺杂-Na0.67Ni0.33Mn0.37Ti0.3O1.9F0.1表现出优异的电化学性能,提供169mAh/g放电容量。在2C的电流密度下进行充放电循环试验,样品不仅提供了119mAh/g的可逆容量,而且在500次充放电循环后的容量保持率为71%。Ti掺杂和表面涂覆富Mn壳显示出提高放电比容量,阴极材料的循环稳定性和倍率能力,并减轻电压衰减。这些结果验证了我们的设计原理,并提供了一种新颖的方法来增强钠离子电池中正极材料的性能。
    We propose a synergistic strategy of titanium doping and surface coating with a Mn-rich shell to modify the Na-rich manganese-oxide-based cathode material Na0.67Ni0.33Mn0.67-xTixO1.9F0.1 in sodium-ion batteries and elucidate the underlying mechanism for enhanced material performance. First, it is found that the electrochemical performance of the proposed cathode material can be effectively improved when the Ti doping amount is x = 0.3. In addition to doping, the cathode material coated with a manganese-rich shell was prepared by a liquid coating method. The as-prepared Mn@Ti-doped-Na0.67Ni0.33Mn0.37Ti0.3O1.9F0.1 exhibited excellent electrochemical performance, delivering 169 mAh/g discharge capacity. The charge-discharge cycle test was carried out at a current density of 2C, and the sample not only provides a reversible capacity of 119 mAh/g but also has a capacity retention rate of 71 % after 500 charge-discharge cycles. The Ti doping and surface coating with a Mn-rich shell are shown to improve the specific discharge capacity, cycling stability and rate capability of the cathode material and mitigate voltage decay. These results validate our design principle and provide a novel approach to enhance the performance of cathode materials in sodium-ion batteries.
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  • 文章类型: Journal Article
    在这项研究中,制备了具有Sb2O3传感膜的电解质-绝缘体-半导体(EIS)电容器。结果表明,掺杂Mg和掺杂Ti的Sb2O3膜经过适当的退火处理后,材料质量和传感性能均得到了改善。在Sb2O3传感膜上进行了Mg掺杂和Ti掺杂的多种材料表征和传感测量,包括X射线衍射(XRD),X射线光电子能谱(XPS)和透射电子显微镜(TEM)。这些详细的研究表明,可以通过掺杂和退火来抑制膜中的硅酸盐和缺陷。此外,致密性增强,结晶和粒化,增强了膜上的表面位置并提高了感应系数,可以通过掺杂和退火来实现。在所有的样本中,在400°C下退火的Mg掺杂膜具有最优选的材料特性和传感行为。基于Mg掺杂的Sb2O3并进行适当退火有望用于未来的工业离子传感设备以及与基于Sb2O3的半导体器件的可能集成。
    In this research, electrolyte-insulator-semiconductor (EIS) capacitors with Sb2O3 sensing membranes were fabricated. The results indicate that Mg doping and Ti-doped Sb2O3 membranes with appropriate annealing had improved material quality and sensing performance. Multiple material characterizations and sensing measurements of Mg-doped and Ti doping on Sb2O3 sensing membranes were conducted, including of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). These detailed studies indicate that silicate and defects in the membrane could be suppressed by doping and annealing. Moreover, compactness enhancement, crystallization and grainization, which reinforced the surface sites on the membrane and boosted the sensing factor, could be achieved by doping and annealing. Among all of the samples, Mg doped membrane with annealing at 400 °C had the most preferable material properties and sensing behaviors. Mg-doped Sb2O3-based with appropriate annealing are promising for future industrial ionsensing devices and for possible integration with Sb2O3-based semiconductor devices.
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  • 文章类型: Journal Article
    Transition-metal sulfides (TMSs) are attractive oxygen evolution reaction (OER) electrocatalysts. Developing new strategies to improve their electrochemical performance of TMSs is of great significance. Herein, a unique pacman-like titanium-doped cobalt sulfide hollow superstructure (Ti-CoSx HSS) is fabricated as an OER electrocatalyst. Using a prearranged metal-organic framework (MOF)-on-MOF heterostructure as a precursor treated by one-pot sulfidation, a sequential structural conversion process leads to the formation of Ti-CoSx HSS, which is assembled by interconnected Ti-doped CoSx nanocages around a cake-like cavity. Benefiting from the architecture and compositional advantages, Ti-CoSx HSS exhibits excellent OER performance with an overpotential of 249 mV at 10 mA cm-2 and Tafel slope of 45.5 mV dec-1 due to increased active site exposure, enhanced electron and mass transfer. This strategy enabled by MOF-on-MOF paves the way toward innovative MOF derivatives for various applications.
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  • 文章类型: Journal Article
    Highly photoactive FeVO4 photoanodes with ordered nanoblock morphology and uniform Ti-doping were prepared by drop-casting mixed Ti and V precursors onto FeOOH nanorod films and following an annealing process. The results indicate that Ti4+ is uniformly doped into the FeVO4 lattice by substituting V5+ and provides an increased number of O2- vacancies. The optimized film thickness and doping level are 620 nm and 0.3%, respectively. Compared to the undoped sample, the Ti-doped photoanode showed ~ 219% enhancement in photocurrent at 1.0 V vs Ag/AgCl under back illumination of AM 1.5, reaching a state-of-the-art value of ~ 1.47 mA cm-2, and also achieved stable and efficient overall water splitting activity with evolution rates of 28.3 and 14.1 μmol cm-2h-1 for H2 and O2, respectively. The excellent PEC performance could be attributed to the remarkably enhanced charge carrier concentration and conductivity, and the facilitated charge transfer kinetics across the semiconductor/electrolyte interface, as a result of Ti-doping.
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