Enhanced Thermoelectric Performance of Non-equilibrium Synthesized Fe_(0.4)Co_(3.6)Sb_(12-x)Ge_x Skutterudites via Randomly Distributed Multi-scaled Impurity Dots

The p-type Ge doped Fe_(0.4)Co_(3.6)Sb_(12-x)Ge_x skutterudites with multi-scaled impurity dots(500 nm-2 mm) were successfully prepared by using melt-quenching(MQ) and subsequent spark plasma sintering(SPS) technique. Compared with traditional method, the new technology significantly shortened the processing time from several days to less than 24 hours. The phase of impurity dots was demonstrated to be CoSb through analysis of X-ray diffraction(XRD) and energy-dispersive spectrum(EDS). Impurity dots were induced by Ge substitution of Sb in the non-equilibrium synthesized process. Due to the abandonment of the long reaction of annealing crystallization, a few of Ge atoms would fail to substitute Sb site of skutterudite in this non-equilibrium synthesized process, leading to that the multi-scaled impurity dots randomly distributed in the matrix of skutterudite Fe_(0.4)Co_(3.6)Sb_(12-x)Ge_x. The combination of multi-scaled impurity dots scattering long wavelength heat-carrying phonons and the point defect scattering short and middle wavelength heat-carrying phonons dramatically made the 22.2% reduction of lattice thermal conductivity. As a result, compared with unsubstituted sample of Fe_(0.4)Co_(3.6)Sb_(12), the maximum ZT value was increased by 30.5%. Thus, the two marked features of this new synthesis process, the shortened preparation time and the enhanced thermoelectric performance, would make a promising commercial application in the future.     

高体积分数的 SiCp/Al复合材料的 SPS致密化机理研究

运用放电等离子烧结（SPS）技术制备出体积分数达60％，致密度达99％的SiCp／Al复合材料．从烧结工艺的控制及电场的影响两方面对SPS烧结SiC，／Al复合材料的机理进行了研究，认为SPS烧结SiCp／Al复合材料的致密化过程主要依靠烧结温度、压力及升温速率的合理搭配，使Al熔融粘结SiC颗粒，而又不溢出模具；烧结过程中未发现明显的放电现象，可能由于电场太弱不足以引发放电．     

Mg2Sn热电粉体的低温固相反应合成及工艺控制

为了解决传统方法制备Mg2X(X=Si、Ge、Sn)基热电材料过程中带来Mg的氧化,挥发,碳化等问题,引进低温固相反应法,成功合成了Mg2Sn粉体,用DTA、XRD、SEM、EDS等分析手段对合成的粉体物相和形貌进行了表征,并系统研究了合成工艺对粉体制备的影响.结果表明:通过改变升温制度可以抑制Mg氧化;调节预压力大小可以有效抑制Sn析出,控制Mg过量可以补偿Mg的挥发;本实验条件下,当Mg过量0.0025mol、预成型压力20MPa、823K下保温8h时,可以得到单相Mg2Sn热电化合物粉体.     

Nanostructuring and thermoelectric properties of bulk N-type Mg<Subscript>2</Subscript>Si

Preparation and thermoelectric properties of nanostructured n-type Mg₂Si bulk materials were reported. Nanosized Mg₂Si powder was obtained by mechanical milling of the microsized Mg₂Si powder prepared by solid-state reaction. The bulk materials with 30 nm and 5 µm were prepared by spark plasma sintering of the nanosized and microsized Mg₂Si powder, respectively. Both the samples show n-type conduction and the Seebeck coefficient of the sintered samples increase determinately with the grain size decrease from 5 µm to 30 nm. On the other hand, the electrical and thermal conductivity decrease with the decrease of grain size. Accordingly, decreasing their grain size increases their thermoelectric-figure-of-merit. A maximum thermoelectric figure of merit of 0.36 has been obtained for the nanostuctured Mg₂Si sample at 823 K, which is 38% higher than that of microsized Mg₂Si bulk materials and higher than results of other literatures. It could be expected that the properties of the nanocomposites could be further improved by doping optimization.     

Mg2Si0.4Sn0.6超微粉体的制备及机理研究

以高纯Mg,Si,Sn粉为原料,采用固相反应合成方法制备得到单相Mg2Si04Sn0.6固溶体粉体,再采用机械球磨的方法对粉体进行细化.利用扫描电子显微镜和X射线衍射仪对不同工艺条件下球磨后的粉体进行形貌及物相分析,研究Mg2Si0.4Sn0.6固溶体球磨过程中颗粒尺寸及组分的变化,认为球磨转速为370 r/min,20:1的球料比,以正己烷为球磨介质,选用WC材质的球磨罐和硬质球,球磨时间30 h,可以得到颗粒尺寸为4～5 μm左右的单相Mg2Si0.4Sn0.6粉体.随着球磨时间的延长,氧化现象加剧,固溶体出现分相,出现MgO和Sn的衍射峰.     

Mg_2Si同质纳微米复合材料的制备及其热电性能

以平均晶粒尺寸约3μm及20 nm的Mg_2Si粉末为原料,采用放电等离子体烧结方法制备出不同纳米、微米含量的Mg_2Si纳微米复合块体材料,系统研究了纳微米结构对材料热电性能的影响.结果表明:随复合材料中纳米颗粒含量的增加,晶界散射增强,导致材料晶格热导率κ_p有明显降低;同时晶界势垒散射的增强也导致Seebeck系数α显著增加,电导率σ有一定程度的降低;综合Seebeck系数α、电导率σ、热导率κ的影响,在纳米颗粒含量为50%(质量分数,下同)、823 K时,获得最大热电优值达0.45,分别是未掺杂纳米相和完全纳米相Mg_2Si材料的1.5及1.1倍.纳微米复合结构的引入,可以获得性能更好的Mg_2Si热电材料.     

SiCp/Al复合材料的SPS烧结及热物理性能研究

采用纯粉末, 通过SPS烧结制备了组织均匀、致密且体积分数高的SiCp/Al电子封装材料. 通过对SPS烧结现象的研究, 认为该复合材料的SPS烧结过程属于反应性烧结, 大部分收缩在极短时间内完成; 另外对SiC体积分数和SiC颗粒尺寸对热导率、热膨胀系数的影响进行了研究, 发现SiC体积分数越高, 复合材料的热导率和热膨胀系数越低; SiC颗粒粒径增大, 复合材料的热导率增高, 而热膨胀系数减小.     

电子探针在Fe-Ni-Cr基合金双极板表面结构研究中的应用

质子膜燃料电池是极具发展潜力的绿色能源,金属双极板取代石墨双极板是燃料电池发展的趋势.但金属双极板耐腐蚀性差,接触电阻高,需要对金属表面进行改性处理.本文采用新型Fe-Ni-Cr合金,对合金双极板进行表面化学改性处理.利用电子探针(EPMA)对改性后的金属双极板表面形貌及成分进行分析,结合不同工艺条件下材料耐腐蚀性能,认为金属表面经改性处理后形成致密氧化膜能提高双极板耐腐蚀性能,电子探针探测金属表面多个微区的氧含量,以及氧含量分布的均匀性,能够合理解释不同工艺条件所引起的耐腐蚀性能的差异.     

Si（111）基片上Mg2Si薄膜的脉冲激光沉积

采用脉冲激光沉积方法在Si(111)基片上制备了Mg2Si薄膜。研究了激光能量密度、退火气氛及压强、退火温度、退火时间等工艺条件对Mg2Si薄膜生长的影响。用X射线衍射仪分析了Mg2Si薄膜的物相,用原子力显微镜、高分辨场发射扫描电镜表征了薄膜的形貌。实验结果表明:在激光能量密度为2.36 J/cm2,Si(111)基片上室温、真空(真空度10-6Pa)条件下沉积,在Ar气压强为10 Pa,500℃,30 min条件下原位退火得到了纯相、结构均匀、表面平整、厚度约为900 nm的Mg2Si多晶薄膜。     

纳米Mg_2Si材料的制备及热电性能研究

以高纯Mg,Si粉合成得到的Mg_2Si微米粉体为原料,采用机械球磨方法制备纳米Mg_2Si粉体。对球磨过程中球磨介质、球料比、转速及球磨时间进行分析,发现:通过机械球磨微米Mg_2Si的方法,以正己烷为球磨介质,选取WC球和罐,在球料比为20:1、转速为370r/min、球磨70h时即可获得平均晶粒尺寸约为十几纳米的Mg_2Si纳米粉体。采用放电等离子体烧结(SPS)烧结纳米Mg_2Si粉体,块体晶粒长大,但仍在100nm左右;由于晶界散射作用,纳米块体Mg_2Si热导率明显降低,电导率、Seebeck系数一定程度下降,综合热电三因素,纳米Mg_2Si块材在800K时获得最大ZT值,为0.36,明显优于微米块体材料。