电化学制备Bi2Te3纳米线用于微型温差发电器

借助于电化学沉积的方法,在氧化铝纳米孔内生长Bi2Te3材料,从而形成温差电纳米线阵列．利用SEM,XRD and TEM分析手段对制备的纳米线形貌和结构进行了分析,测量了纳米线的组成和温差电性能．p型和n型Bi2Te3纳米线材料的Seebeck系数经过测量分别为260μV／K和-188μV／K（307K）,比同类的块状温差电材料性能高．同时研究了沉积电位对氧化铝模板中纳米孔的填充率的影响,并对纳米线阵列的电阻进行了测量．尝试了利用n型和P型Bi2Te3纳米线阵列制备一种新型的微型温差发电器．     

Heterogeneous Single-Atom Catalysts for Electrochemical CO2 Reduction Reaction

The electrochemical CO₂ reduction reaction (CO₂RR) is of great importance to tackle the rising CO₂ concentration in the atmosphere. The CO₂RR can be driven by renewable energy sources, producing precious chemicals and fuels, with the implementation of this process largely relying on the development of low-cost and efficient electrocatalysts. Recently, a range of heterogeneous and potentially low-cost single-atom catalysts (SACs) containing non-precious metals coordinated to earth-abundant elements have emerged as promising candidates for the CO₂RR. Unfortunately, the real catalytically active centers and the key factors that govern the catalytic performance of these SACs remain ambiguous. Here, this ambiguity is addressed by developing a fundamental understanding of the CO₂RR-to-CO process on SACs, as CO accounts for the major product from CO₂RR on SACs. The reaction mechanism, the rate-determining steps, and the key factors that control the activity and selectivity are analyzed from both experimental and theoretical studies. Then, the synthesis, characterization, and the CO₂RR performance of SACs are discussed. Finally, the challenges and future pathways are highlighted in the hope of guiding the design of the SACs to promote and understand the CO₂RR on SACs.     

Bi2Te3基热电材料的研究现状及发展

热电材料是能将热能和电能直接相互转化的功能材料,它的出现为解决能源紧缺和环境污染提供了广阔的应用前景.从理论和实验两个方面对Bi2Te3基热电材料近年来国内外的研究现状及发展进行了简要介绍和评述,并指出了今后的发展方向.在理论上主要基于能带理论、半导体超晶格以及密度泛函理论去寻求影响该材料的相关因子,在实验上主要采用分子束外延、激光脉冲沉积、合金化和水热合成法等方法制备该热电材料.     

湿化学方法制备纳米Bi2Te3系热电材料的研究进展

热电材料因自身的优点而受到人们的广泛重视,但热电性能普遍不高成为制约其进一步应用的关键.随着热电理论和纳米技术的不断发展,纳米热电材料的研究成为近年来热电领域的一大热点.在分析介绍国内外湿化学方法制备纳米Bi2Te3系热电材料研究现状的基础上,指出了各种方法的优缺点,并展望了纳米热电材料的制备及其应用发展趋势.     

Bi2Te3基热电薄膜材料的制备方法研究

Bi2Te3基热电材料由于在微电子、光电子等高技术领域具有潜在的应用前景,从而得到了人们的广泛关注.低维Bi2Te3基热电材料由于具有特殊的量子限制效应,已成为提高热电性能的有效途径.近年来,研究者非常重视Bi2Te3基热电薄膜的制备及性能研究,并做了大量相关的研究工作,许多制备方法也相继出现,并获得了高质量的Bi2Te3基热电薄膜.     

气相传输法制备大尺寸单晶Bi2Se3纳米片、纳米带

低维Bi₂Se₃纳米材料是最新研究发现的一种新型三维拓扑绝缘体材料, 在微电子器件和传感器领域具有广阔的应用前景。本研究采用气相传输法在真空石英管中合成了大尺寸单晶Bi₂Se₃纳米片、纳米带。通过XRD、EDS、Raman、SEM等手段对Bi₂Se₃纳米片、纳米带的物相结构、组成、表面形貌等进行表征。测试结果表明: 气相传输法合成的单晶Bi₂Se₃纳米片、纳米带相纯度高, 结晶性能好, 均是{001}取向; Bi₂Se₃纳米片水平尺寸大, 约为15~180 μm; Bi₂Se₃纳米带长度达860 μm, 宽度约5 μm。根据不同温度下制备的Bi₂Se₃纳米片、纳米带SEM照片及其不同方向结合能的差异, 分析了其可能的生长机制: 在较高温度下沿<001>和方向生长速度快, 生成大尺寸单晶Bi₂Se₃纳米片; 在较低温度下, 沿方向生长速度快, 生成大尺寸单晶Bi₂Se₃纳米带。这些研究结果完善了大尺寸Bi₂Se₃纳米材料的制备工艺, 有望在微电子器件领域得到商业化应用。     

超声波-水热法合成Bi2Te3纳米管

以水为反应介质，NaBH4为还原剂，合成了BizTe3纳米管及纳米微粒。溶液首先在超声波发生器中预处理1h，然后置于150℃，水热反应釜中继续反应48h。XRD分析表明：合成产物主要物相为Bi2Te3；SEM观察可见产物中有纳米管生成，纳米管直径约为50-100nm，管壁厚约8-10nm，长度在500nm以上。EDS分析表明：纳米管成份为Bi2Te3。Bi2Te3纳米管可能的生长机制为纳米薄片-卷曲-闭合-纳米管。     

电化学沉积Bi_2Te_3薄膜及其发电器件的制备

通过控制不同梯度的电流密度和电沉积时间,利用电化学方法在铜片上沉积Bi/Te薄膜,经不同温度退火处理后生成Bi2Te3;采用SEM(带EDS)和XRD对薄膜的形貌、成分进行分析,研究了电流密度和电沉积时间对晶粒成长的影响,并对用Bi2Te3薄膜制成发电器件的性能进行了研究。结果表明:电流密度越大,Bi2Te3晶粒尺寸越小;电沉积的时间越长,Bi2Te3薄膜越均匀;退火过程中350℃结晶效果最好;退火后可以形成多晶薄膜,颗粒致密均匀,具有一定择优取向性,还可以提高Seebeck系数,达到-123μV/K;对比传统块状粒子发电,电化学沉积制备的Bi2Te3薄膜发电器件更具有优势。     

Bi_2Te_3/炭黑复合材料的制备及热电性能

采用水热法合成Bi_2Te_3粉体,将炭黑(CB)与其掺杂制备不同比例的碲化铋/炭黑(Bi_2Te_3/CB)复合材料,研究复合材料的热电性能。同时采用TGA、SEM、XRD等分析方法表征Bi_2Te_3/CB复合材料的结构,探究微观结构与热电性能的关系。研究发现:室温下,CB的引入使Bi_2Te_3/CB复合材料的热导率大大降低(0.5957 W/(m·K)降到0.0888 W/(m·K));随着Bi_2Te_3含量的增加,复合材料的电导率、热导率均增大,Seebeck系数先增加后降低;当Bi_2Te_3含量为88.9%时,在558℃烧结10min所得的Bi_2Te_3/CB复合材料室温下热电优值ZT最大(ZT=0.21)。虽然ZT值未能达到应用价值,但是CB的添加为改善Bi_2Te_3材料的热电性能,尤其在降低材料的热导率方面,提供了新方法和新思路。     

放电等离子烧结制备的Bi2Te3／Sb2Te3复合材料的热电性能

研究了用低温湿化学法和水热法制备纳米级的Bi2Te3和sb挪e3颗粒，并通过透射电镜观察其微观形貌。Bi2Te3粉末的微观形貌为直径在30-50n之间的片状小颗粒，而sb2Te3颗粒的微观形貌为薄带状，直径约为70nm，长度则为从150-300nm不等，并对其晶体的形核和长大机理进行了讨论。认为，纳米小颗粒状的Bi2Te3晶体可能是通过“表面形核和侧向生长”形成的产物，而薄带状的sb2Te3晶体可能是在Te块解体形成的条带状碎屑基础上形成的。用放电等离子烧结法（spark plasma sintering）制备不同比例的Bi2Te3／Sb2Te3块状复合材料，测量并比较了其热电性能。通过改变Bi2Te3的量，可以提高复合材料的电性能。成分不同的层片间的散射，能更有效地降低块体材料的热导率。在500K的温度下，Bi2Te3和sb2Te3以摩尔比为1：1复合烧结的试样的热导率低达0．7W／（m·K）。进一步优化Bi2Te3和sb2Te3的复合比例，其热电性能可能会有进一步的提高。     

Te-seeded growth of few-quintuple layer Bi2Te3 nanoplates

We report on a Te-seeded epitaxial growth of ultrathin Bi2Te3 nanoplates （down to three quintuple layers （QL）） with large planar sizes （up to tens of micrometers） through vapor transport. Optical contrast has been systematically investigated for the as-grown Bi2Te3 nanoplates on the SiO2/Si substrates, experimentally and computationally. The high and distinct optical contrast provides a fast and convenient method for the thickness determination of few-QL Bi2Te3 nanoplates. By aberration-corrected scanning transmission electron microscopy, a hexagonal crystalline structure has been identified for the Te seeds, which form naturally during the growth process and initiate an epitaxial growth of the rhombohedral- structured Bi2Te3 nanoplates. The epitaxial relationship between Te and Bi2T% is identified to be perfect along both in-plane and out-of-plane directions of the layered nanoplate. Similar growth mechanism might be expected for other bismuth chalcogenide layered materials.     

射频磁控溅射制备Bi2Te3热电薄膜

通过射频磁控溅射，在溅射气体为Ar，气压为1Pa，溅射功率为120W时分别在聚氨酯和玻璃基底上沉积了不同厚度的Bi2Te3薄膜。Bi2Te3薄膜主要是以（221）晶面平行于基底进行外延生长，先在基底形成大量微小晶粒，合并长大成典型的纤维状组织结构。在此条件下薄膜生长速率为26nm/min，通过控制溅射时间可沉积几纳米到几微米不同厚度的薄膜。得到的p-型半导体Bi2Te3薄膜，其电阻率随薄膜厚度的增大而减小。     

Bi2Te3基可穿戴温差发电器件的制备及性能

利用人体体温发电的热电器件因其结构简单、可靠性高,有望为可穿戴电子产品等低功耗设备提供免维护、长期稳定的能源。以高性能无机块体热电材料和低热导环氧树脂/玻璃微珠复合粘结剂作为原料,采用切割粘结法和磁控溅射/电化学镀铜技术,制备了热电臂高度不同的48对温差发电器件。由于该技术不需使用陶瓷覆铜板,在给定的器件厚度条件下,可提高热电臂高度。性能表征结果显示,在实际穿戴条件下,随热电臂高度的增加,器件的输出功率密度持续增加。在相当于一级风的空气对流条件下或正常行走状态下,热电臂高度为3.14mm的器件输出功率密度超过40μW/cm²。     

热塑形方法制备N型Bi2Te3材料

本文介绍了采用热塑形方法制备N型Bi2Te3温差电材料.并且给出了所获得样品的密度、抗弯强度、SEM以及温差电性能(包括电导率和塞贝克系数)的测试结果.实验结果表明,在最佳的热塑形工艺下制备的样品的功率因子与区熔材料相当,但其机械强度要明显优于区熔材料.热压塑形样品在垂直于塑形压力的方向上具有良好的取向,并且样品在此方向上的功率因子远远大于其在平行压力方向上的功率因子值.     

Density-Dependence of Surface Transport in Tellurium-Enriched Nanograined Bulk Bi2Te3

Three-dimensional topological insulators (3D TI) exhibit conventional parabolic bulk bands and protected Dirac surface states. A thorough investigation of the different transport channels provided by the bulk and surface carriers using macroscopic samples may provide a path toward accessing superior surface transport properties. Bi₂Te₃ materials make promising 3D TI models; however, due to their complicated defect chemistry, these materials have a high number of charge carriers in the bulk that dominate the transport, even as nanograined structures. To partially control the bulk charge carrier density, herein the synthesis of Te-enriched Bi₂Te₃ nanoparticles is reported. The resulting nanoparticles are compacted into nanograined pellets of varying porosity to tailor the surface-to-volume ratio, thereby emphasizing the surface transport channels. The nanograined pellets are characterized by a combination of resistivity, Hall- and magneto-conductance measurements together with (THz) time-domain reflectivity measurements. Using the Hikami-Larkin-Nagaoka (HLN) model, a characteristic coherence length of ≈200 nm is reported that is considerably larger than the diameter of the nanograins. The different contributions from the bulk and surface carriers are disentangled by THz spectroscopy, thus emphasizing the dominant role of the surface carriers. The results strongly suggest that the surface transport carriers have overcome the hindrance imposed by nanoparticle boundaries.     

Bi_2Te_3柔性热电薄膜发电器件

在几种形状不同的柔性电路板上磁控溅射Bi_2Te_3薄膜,温差测试之后进行结构的优化设计。在给予一定温差条件下,测量优化设计后的柔性热电薄膜在退火前后的输出电压和电阻率,并提出了改进措施。研究表明:优化后的柔性热电薄膜相较之前有很大的改善;柔性热电薄膜输出的电压与提供的温差近似呈线性关系;在温差为200K时,输出电压为310mV,电阻率为0.792mΩ·cm;200℃/h真空退火后,输出电压增大到368mV,电阻率也同时增大,达到0.869mΩ·cm。     

Modulation of Vacancy Defects and Texture for High Performance n-Type Bi2Te3 via High Energy Refinement

The carrier concentration in n-type layered Bi₂Te₃-based thermoelectric (TE) material is significantly impacted by the donor-like effect, which would be further intensified by the nonbasal slip during grain refinement of crushing, milling, and deformation, inducing a big challenge to improve its TE performance and mechanical property simultaneously. In this work, high-energy refinement and hot-pressing are used to stabilize the carrier concentration due to the facilitated recovery of cation and anion vacancies. Based on this, combined with SbI₃ doping and hot deformation, the optimized carrier concentration and high texture degree are simultaneously realized. As a result, a peak figure of merit (zT) of 1.14 at 323 K for Bi₂Te_2.7Se_0.3 + 0.05 wt.% SbI₃ sample with the high bending strength of 100 Mpa is obtained. Furthermore, a 31-couple thermoelectric cooling device consisted of n-type Bi₂Te_2.7Se_0.3 + 0.05 wt.% SbI₃ and commercial p-type Bi_0.5Sb_1.5Te₃ legs is fabricated, which generates the large maximum temperature difference (ΔT_max) of 85 K at a hot-side temperature of 343 K. Thus, the discovery of recovery effect in high energy refinement and hot-pressing has significant implications for improving TE performance and mechanical strength of n-type Bi₂Te₃, thereby promoting its applications in harsh conditions.     

Selective Dissolution-Derived Nanoporous Design of Impurity-Free Bi2Te3 Alloys with High Thermoelectric Performance

Thermoelectric technology, which has been receiving attention as a sustainable energy source, has limited applications because of its relatively low conversion efficiency. To broaden their application scope, thermoelectric materials require a high dimensionless figure of merit (ZT). Porous structuring of a thermoelectric material is a promising approach to enhance ZT by reducing its thermal conductivity. However, nanopores do not form in thermoelectric materials in a straightforward manner; impurities are also likely to be present in thermoelectric materials. Here, a simple but effective way to synthesize impurity-free nanoporous Bi_0.4Sb_1.6Te₃ via the use of nanoporous raw powder, which is scalably formed by the selective dissolution of KCl after collision between Bi_0.4Sb_1.6Te₃ and KCl powders, is proposed. This approach creates abundant nanopores, which effectively scatter phonons, thereby reducing the lattice thermal conductivity by 33% from 0.55 to 0.37 W m⁻¹ K⁻¹. Benefitting from the optimized porous structure, porous Bi_0.4Sb_1.6Te₃ achieves a high ZT of 1.41 in the temperature range of 333–373 K, and an excellent average ZT of 1.34 over a wide temperature range of 298–473 K. This study provides a facile and scalable method for developing high thermoelectric performance Bi₂Te₃-based alloys that can be further applied to other thermoelectric materials.     

Giant Peak Voltage of Thermopower Waves Driven by the Chemical Potential Gradient of Single‐Crystalline Bi2Te3

The self‐propagating exothermic chemical reaction with transient thermovoltage, known as the thermopower wave, has received considerable attention recently. A greater peak voltage and specific power are still demanded, and materials with greater Seebeck coefficients have been previously investigated. However, this study employs an alternative mechanism of transient chemical potential gradient providing an unprecedentedly high peak voltage (maximum: 8 V; average: 2.3 V) and volume‐specific power (maximum: 0.11 W mm^?3; average: 0.04 W mm^?3) using n‐type single‐crystalline Bi₂Te₃ substrates. A mixture of nitrocellulose and sodium azide is used as a fuel, and ultraviolet photoelectron spectroscopy reveals a significant downshift in Fermi energy (≈5.09 eV) of the substrate by p‐doping of the fuel. The induced electrical potential by thermopower waves has two distinct sources: the Seebeck effect and the transient chemical potential gradient. Surprisingly, the Seebeck effect contribution is less than 2.5% (≈201 mV) of the maximum peak voltage. The right combination of substrate, fuel doping, and anisotropic substrate geometry results in an order of magnitude greater transient chemical potential gradient (≈5.09 eV) upon rapid removal of fuel by exothermic chemical reaction propagation. The role of fuel doping and chemical potential gradient can be viewed as a key mechanism for enhanced heat to electric conversion performance.