两元P-型梯度结构热电材料FeSi_2/Bi_2Te_3的制备与性能

采用热浸焊法用纯Sn作为过渡层制备了P 型FeSi2 /Bi2 Te3 梯度结构热电材料并对其热电性能进行了测试。发现当热端温度在 5 10℃以下时 ,梯度结构热电材料的平均Seebeck系数保持恒定 ,达 2 2 0 μV/K至 2 5 0μV/K左右 ,显著高于单一均质材料 (Bi2 Te3 和 β FeSi2 )在相同温度范围内的平均Seebeck系数。梯度结构热电材料的输出功率较单种材料高 1.5至 2倍以上 ,且当材料经 190℃ ,10 0h与 2 0 0h的真空退火后 ,输出功率几乎不变。金相观察表明 ,在Sn层与两半导体界面处 ,没有明显的Sn扩散迹象 ,说明在所试验的条件下 ,用Sn作为过渡层热稳定性较好。     

宽温区P-型热电材料的性能表征与设计

通过对Bi2 Te3 /FeSi2 叠层热电材料的性能建模计算 ,得出了该结构的平均Seebeck系数及内电阻与热端温度的关系可分别用两个三次多项式表征。在外阻为 0 .0 734Ω ,热端温度约 5 10℃时 ,Bi2 Te3 /FeSi2 叠层热电材料的最大输出功率值与实验值较为接近 ,在相同条件下均为计算得出的单段FeSi2 材料的 2 .5倍 ,说明该方法有效、可行。对用此方法建模设计多种单段材料组合成的梯度结构 ,计算发现以两种不同成分并经相近工艺制备的均质FeSi2 材料制成的叠层结构性能较优 ,与Bi2 Te3 /FeSi2 结构有相同的最大输出功率值。但从多方面分析表明 ,用两均质FeSi2 材料制成的宽温区热电材料更具潜力     

Bi_2Te_3和Bi_(0.5)Sb_(1.5)Te_3的机械合金化法制备及其热电性能

用机械合金法制备了Bi2 Te3和Bi0 .5Sb1 .5Te3两种热电材料。XRD分析表明两种材料分别在球磨 1 75h和 31 5h后完全合金化。机械合金化合金粉末冷压后在不同温度烧结并测量了热电性能 ,其中Bi0 .5Sb1 .5Te3材料480℃烧结样的最高Seebeck系数约为 2 0 0 μV/K。     

p—型FeSi2／Bi2Te3梯度热电材料的优值推证与界面温度优化

通过对两元 p-型梯度热电材料 Fe Si2 / Bi2 Te3界面温度的建模计算与实验验证 ,在固定热冷端温区内积分得出的 Z- ΔT值与界面温度 Ti 的关系曲线为 :Z- ΔT =0 .6 72 +11.7× 10 - 4Ti - 1.31× 10 - 6 T2i - 3.4 9× 10 - 9T3i该关系可用来表征两元梯度结构的热电性能。从拟合曲线上得出该梯度结构的最佳界面温度为 2 2 0℃～ 2 30℃ ,这与实验测出两单段材料 (Fe Si2 ,Bi2 Te3)长度比为 10∶ 1左右时所形成的界面温度较为接近。通过测试不同长度比的材料输出功率 ,也发现 10∶ 1梯度材料的最大输出功率较大 ,是相同温差下单段 β- Fe Si2 材料的 2倍～ 2 .6倍。     

溶剂热合成Bi2Te3基合金的结构与电学性能

用溶剂热法合成了二元Bi2Te3和三元Bi1.3Sn0.7Te3合金纳米粉末,并采用热压技术制备了块状热电材料.XRD分析结果表明:Bi-Sn-Te三元固溶体合金可以直接通过溶剂热合成获得单相产物,而非掺杂Bi2Te3合金需要通过热压等后热处理来实现产物的单一化;热压过程有助于促进反应的完全和晶型的完整,但会导致晶粒的长大.对试样电导率σ和Seebeck系数α的测量结果显示,Bi-Sn-Te三元固溶体合金比二元Bi-Te合金具有更好的电学性能.     

采用Sn-Bi钎料钎焊Bi2Te3基热电材料与无氧铜

Bi2Te3基热电材料需与电极Cu连接构成热电模块.采用无铅钎料Sn-Bi及钎剂实现了大气环境中分别直接钎焊p型(Bi,Sb)2Te3与无氧Cu和n型Bi2(Te,Se)3与无氧Cu.观察了接头的组织及Sn,Cu,Bi元素在接头处的线分布和面分布.通过研究表明,Sn元素与p型(Bi,Sb)2Te3的反应比与n型Bi2(Te,Se)3剧烈,在(Bi,Sb)2Te3与Sn-Bi界面处形成了5～7 μm的Sn反应层;Cu元素在Cu/Sn-Bi界面处也形成几微米的反应层;温度增加,两种反应的程度均有增加趋势.利用Gleeble1500D试验机测试了两种类型接头的抗剪强度,结果表明,(Bi,Sb)2Te3/Sn-Bi/Cu接头平均抗剪强度为5.1MPa,Bi2(Te,Se)3/Sn-Bi/Cu接头则为4.4 MPa,(Bi,Sb)2Te3/Sn-Bi/Cu接头强度分散性高于Bi2(Te,Se)3/Sn-Bi/Cu接头.接头主要断裂于反应层,反应层的成分、组织和厚度是影响接头强度的关键因素.     

热电材料研究最新动向

<正>目前块状热电材料无量纲指数ZT最大值为0.8,最大热电转换效率不到10%。典型热电材料有PbTe3、Bi2Te3、PbTe及Si-Ge等合金。Bi2Te3用于室温附近,PbTe用于300℃,Si-Ge用于800℃以上。PbTe属于NaCl型结构,离子键很强,在Pb节点以Sn置换,禁带宽度发生变化,由于Pb和Sn的合金化散     

机械合金化法制备的Mn15Bi34Te51和La15Bi34Te51热电材料

用机械合金化法制备了Mn15Bi34Te51和La15Bi34Te51合金，XRD分析表明Mn15Bi34Te51和La15Bi34Te51分别在真空球磨150h和100h后实现合金化，La15Bi34Te51在真空球磨150h后形成了纳米结构的合金，镧原子的加入有助于Bi2Te3基合金的晶粒细化及非晶化。对La15Bi34Te51合金的XRD结构分析表明镧原子有可能进入了Bi2Te3层状结构的Te-Te原子层间。La15Bi34Te51合金Seebeck系数的测量表明当晶粒尺寸减小到纳米尺寸时，载流子散射机制有可能发生改变，导致了Seebeck系数的大幅上升。     

PEDOT:PSS(聚3,4-乙撑二氧噻吩/聚苯乙烯磺酸盐)/ Bi0.5Sb1.5Te3复合材料热电性能研究

将PEDOT:PSS(聚3,4-乙撑二氧噻吩/聚苯乙烯磺酸盐)与Bi0.5Sb1.5Te3粉末混合烘干,在液氮下研磨成粉,将粉末经过热压工艺致密化,获得复合热电材料。通过XRD和FESEM表征其相结构和微观形貌,对该样品的电传输性能和热传输性能进行测试,结果表明：在75℃时,质量比90%的Bi0.5Sb1.5Te3复合PEDOT:PSS样品ZT值为0.1,比纯PEDOT:PSS样品高出40倍;复合材料样品Seebeck系数随着Bi0.5Sb1.5Te3的增加大幅提升,无机相连续分布是提高复合材料Seebeck系数的关键。     

Ga、K双掺杂对N型Bi_2Te_(2.7)Se_(0.3)材料热电性能的影响

采用真空熔炼及热压方法制备了Ga和K双掺杂N型Bi2Te2.7Se0.3热电材料。XRD分析结果表明,Ga和K已经完全固溶到Bi2Te2.7Se0.3晶体结构中,形成了单相固溶体合金。SEM分析表明,材料组织致密且有层状结构特征。通过Ga和K部分替代Bi,在300~500 K的大部分温度范围内,Ga和K双掺杂对提高Bi2Te2.7Se0.3的Seebeck系数产生了积极的作用,同时双掺杂样品的电导率也得到明显的提高。Ga和K双掺杂样品的热导率都大于未掺杂的Bi2Te2.7Se0.3,Ga0.02Bi1.94K0.04Te2.7Se0.3合金在500 K获得ZT最大值为1.05。     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

Crystal structures and structural relationships of KFe2(SeO2OH)(SeO3)3 and SrCo2(SeO2OH)2(SeO3)2

The new phases KFe₂(SeO₂OH)(SeO₃)₃ and SrCo₂(SeO₂OH)₂(SeO₃)₂ have been synthesized under low-hydrothermal conditions and their structures were determined by single-crystal X-ray methods. Both compounds are monoclinic; KFe₂(SeO₂OH)(SeO₃)₃: space group P2, A = 9.983(4), B = 5.270(1), C = 10.614(4) Å, β = 97.42(2)°, V = 553.7 ų, Z = 2; SrCo₂(SeO₂OH)₂(SeO₃)₂: space group P2ln, A = 14.984(2), B = 5.286(1), C = 13.790(2) Å, β = 94.72(1)°, V = 1088.5 ų , Z = 4. The refinements converged to R-values of 2.9 and 3.6% respectively.

The atomic arrangement in KFe₂(SeO₂OH)(SeO₃)₃ and SrCo₂(SeO₂OH)₂(SeO₃)₂ is based on isolated MO₆ octahedra (M = Fe³⁺, Co²⁺), which are corner-linked via trigonal pyramidal selenite groups to a framework structure. Interstitials are occupied by potassium or strontium atoms in ten- or eight-coordination respectively, and by the lone-pair electrons of the Se⁴⁺ atoms. Both compounds are not isotypic but are closely related and may be interpreted as different distortions of an idealized structure type in space group P2/m, which was modelled for a theoretical compound SrFe₂(SeO₃)₄ by distance least squares refinement (program ).     

MoS2 coated with Al2O3 for Ni-MoS2/Al2O3 composite coatings by pulse electrodeposition

The MoS₂ powders were coated with Al₂O₃ (5 wt.%) through controlling hydrolysis of Al (NO₃)₃·9H₂O. MoS₂ powder coated with Al₂O₃ was written as MoS₂/Al₂O₃ hereinafter. MoS₂/Al₂O₃ powders were put into Ni plating electrolyte bath. Cetyltrimethylammonium bromide (CTAB) — the surfactant was also put into the bath. The experiment proves that MoS₂/Al₂O₃ particles were absorbed onto the Ni plate. The amount of MoS₂/Al₂O₃ deposited on Ni plate rises with the increasing concentration of MoS₂/Al₂O₃ in the bath. The microhardness, micro-surface, phase and the tribological property of the MoS₂/Al₂O₃ multi-plating coating were measured and analyzed. The performances of microhardness and wear resistance of the Ni-MoS₂/Al₂O₃ composite are better than those of Ni-MoS₂ composite.     

Corrosion characteristics of LiBH4 film exposed to a CO2/H2O/O2/N2 mixture

LiBH₄ films were prepared by pulsed laser deposition using a LiB target in a background pressure of hydrogen. The corrosion characteristics of LiBH₄ films were measured by exposing them to a gas mixture of CO₂/H₂O/O₂/N₂ at ambient temperature for 1–24 h. Scanning electron microscopy images show some cracks on the surface of corrosion films, which could act as easy paths for H₂O and CO₂ to further react with Li⁺ and B³⁺. The X-ray photoelectron spectroscopy results and theoretical analysis show that LiBH₄ tends to react with H₂O and CO₂ to form Li₂B₄O₇, Li₂CO₃ and LiOH during the corrosion process.     

Synthesis and properties of CaCd2Sb2 and EuCd2Sb2

High density polycrystalline CaCd₂Sb₂ and EuCd₂Sb₂ intermetallics are synthesized by Spark Plasma Sintering and their thermoelectric properties are investigated. X-ray diffraction measurements reveal both materials have a structure in space group, containing a small amount of CdSb as a second phase. Thermoelectric measurements indicate both are p-type conductive materials. The figure of merit value of CaCd₂Sb₂ is 0.04 at 600 K and that of EuCd₂Sb₂ is 0.60 at 617 K. Theoretical calculations show that CaCd₂Sb₂ is a degenerate semiconductor with a band gap of 0.63 eV, while EuCd₂Sb₂ is metallic with DOS of 13.02 electrons/eV. For deeper understanding of the better thermoelectric properties of EuCd₂Sb₂, its low temperature magnetic, transport and heat capacity properties are investigated. Its Nèel temperature is 7.22 K, convinced by heat capacity anomaly at 7.13 K. Hall effect convinced that it is a p-type conductive material. It has high Hall coefficient, high carrier concentration and high carrier mobility of +1.426 cm³/C, 4.38 × 10¹⁸/cm³ and 182.40 cm²/Vs, respectively. They are all in the magnitude of good thermoelectric materials. The Eu 4f level around Fermi energy and antiferromagnetic order may count for the better thermoelectric properties of EuCd₂Sb₂ than that of CaCd₂Sb₂.     

New Zr6CoAs2-type compounds: Y6CoBi2, Ho6CoBi2 and Tm6CoBi2

Results of a powder X-ray diffraction investigation of new ternary compounds are reported. The compounds Y₆CoBi₂ [a=0.8312(1) nm, c=0.4144(1) nm], Ho₆CoBi₂ [a=0.8246(2) nm, c=0.4095(1) nm], and Tm₆CoBi₂ [a=0.8155(2) nm, c=0.4066(1) nm] crystallize in the hexagonal Zr₆CoAs₂-type structure (space group P6b2m No. 189). The Zr₆CoAs₂-type structure is a superstructure of the Fe₂P-type structure.     

Gd Mössbauer effect and magnetic properties of GdNi2Sb2, GdCu2Sb2 and GdAl2Ga2

We have investigated the magnetic properties and the ¹⁵⁵Gd Mössbauer spectra of the ThCr₂Si₂-type compounds GdNi₂Sb₂, GdCu₂Sb₂ and GdAl₂Ga₂. These three compounds were found to order antiferromagnetically, with T_N=6.5 K, 15.8 K, and 42.4 K respectively. The electric field gradient V₂₂ derived from the quadrupole splitting of the Mössbauer spectra gives rise to a sign change at the end of the T3d series in GdT₂Sb₂, as was observed previously also for the corresponding compounds with Si and Ge. This behaviour was explained in terms of decreasing hybridization between the Gd valence electron states and the d electron states of the T atoms.     

等离子球化制备球形CaF2/BaF2共晶粉末*

探究了使用大气等离子喷涂设备制备适合热喷涂使用的球形CaF2/BaF2共晶粉末的可能性。68%BaF2、32%CaF2粉末(质量分数)经过1 100℃真空烧结后,形成致密的块状氟化物共晶。机械破碎后的氟化物共晶经过等离子焰流重熔后得到了球形的氟化物共晶。使用F14-1流动性和松装密度测定仪测量球化前后粉末的流动性和松装密度。采用扫描电子显微镜,XRD表征球化前后粉末的形貌和物相组成。结果表明:球化后的粉末呈现较好的球形,球化后粉末的流动性和松装密度较球化前也有较大的改善:球化后共晶粉末的流动时间为55.20s/50g,松装密度为1.89g/cm3;另外,球化后共晶粉末还表现出良好的高温润滑性能:含有10%CaF2/BaF2共晶(质量分数)的镍基涂层在600℃和800℃的平均摩擦因数都小于0.3。     

Thermal cycle behavior of plasma sprayed La2O3, Y2O3 stabilized ZrO2 coatings

The effects of La₂O₃ addition on thermal conductivity, phase stability and thermal cycle life of Y₂O₃ stabilized ZrO₂ plasma sprayed coatings were investigated. Although low thermal conductivity as well as high resistance to sintering was achieved by La₂O₃ addition, it tended to also result in lower phase stability and thermal cycle life of the coatings. Optimization of the composition and structure of the coatings improved these properties, and the optimized coatings showed prolonged thermal cycle life.     

Crystal structures of VSn2, NbSn2 and CrSn2 with Mg2Cu-type structure and NbSnSb with CuAl2-type structure

Several binary stannides of the early transition metals T have been reported with the composition T₂Sn₃ previously. However, the present structure refinements from single-crystal X-ray data show that they have the compositions VSn₂, NbSn₂ and CrSn₂ (R = 0.028, R = 0.018 and R = 0.021 with 17 variable parameters and 828, 512 and 440 structure factors respectively). Their orthorhombic Mg₂Cu-type structure is closely related to the structures of MoSn₂ (Mg₂Ni type) and CuAl₂. The latter structure type was confirmed for NbSnSb by a structure refinement from single-crystal data (R = 0.010 for eight variables and 254 F values). Electrical conductivity measurements show CrSn₂ and MoSn₂ to be metallic conductors.