制备工艺对Ca_3Co_4O_9/Bi_2Ca_2Co_2O_y复合热电材料组织和性能的影响

采用助熔剂法和固相反应法分别合成了Ca_3Co_4O_9和Bi_2Ca_2Co_2O_y粉体。配比后分别通过冷压、冷等静压、热压三种制备工艺制得组织取向和致密度不同Ca_3Co_4O_9/Bi_2Ca_2Co_2O_y块体复合材料,测量表征了其热电性能和物相形貌。结果表明,冷等静压工艺减弱了材料中颗粒的取向,降低了热导率,973 K时为1.35 W·K~(–1)·m~(–1);热压工艺提高了样品的致密度,降低了电阻率,973 K时功率因子达到了4.0×10~(–4) W·m~(–1)·K~(–2)。     

Ca_3Co_4O_9热电材料前驱体制备及性能表征

分别采用固相反应法和空间俘获法制备了Ca3Co4O9前驱体,并经冷等静压后常压烧结工艺制备了块体陶瓷样品。利用TG-DSC、XRD、SEM等方法对前驱体进行了表征,同时测试了陶瓷样品的热电性能。结果表明:空间俘获法可获得纯相、晶粒较小的前驱粉体,同时降低了合成温度,而且合成样品的Seebeck系数和功率因子明显高于固相反应法。在976 K获得最大Seebeck系数和功率因子分别为179μV/K、7.5×10–7 W/(cm·K2),较固相反应优化60%、16倍;电阻率略有升高。     

La掺杂对Ca_(3-x)La_xCo_(3.9)Cu_(0.1)O_(9+δ)/Bi_2Ca_2Co_(1.9)Cu_(0.1)O_y复合热电材料的性能优化研究

采用助溶剂法和固相反应法分别合成Ca_(3-x)La_xCo_(3.9)Cu_(0.1)O_(9+δ)(0≤x≤0.16)和Bi_2Ca_2Co_(1.9)Cu_(0.1)O_y陶瓷粉体,通过热压烧结制备Ca_(3–x)La_xCo_(3.9)Cu_(0.1)O_(9+δ)/Bi_2Ca_2Co_(1.9)Cu_(0.1)O_y复合热电材料,研究了La掺杂对复合热电材料的微观结构、物相组成和热电性能的影响。结果表明:La掺杂复合热电材料的XRD谱与标准JCPDS卡保持一致,没有引进新的杂质;La掺杂样品的电导率和Seebeck系数同时增加,功率因子得到显著提高。在973 K时,Ca_(2.92)La_(0.08)Co_(3.9)Cu_(0.1)O_(9+δ)/Bi_2Ca_2Co_(1.9)Cu_(0.1)O_y样品的功率因子达到4.477×10~(–4 )W·m~(–1)·K~(–2)。     

低维Bi_2Te_3热电材料的制备与性能研究

用溶剂热法制备了直径在100nm以内的一维针状及厚20～30nm、长几微米的二维花朵状Bi2Te3热电材料,分析了不同形貌产物的生长机理,并对其热电性能进行了比较。结果表明,添加剂的分子结构对产物形貌起决定性作用。不同形貌产物的热电性能随温度变化的机制不同,一维纳米结构Bi2Te3产物的功率因子随温度升高而增加,最大值为143.1μΩ·m–1K–2。而二维纳米结构的Bi2Te3产物虽然在室温附近有较大的Seebeck系数,约100μV/K,但由于其电导率较低,功率因子在较宽的温度范围内保持在23μΩ·m–1K–2左右。     

Ca_3Co_4O_9热电材料的研究进展

由于Ca_3Co_4O_9具有良好的化学稳定性及廉价、无毒等优点,已成为氧化物热电材料研究的热点。但其合成难,致密度低,转换效率低等严重阻碍了Ca_3Co_4O_9的实际应用。该文从合成方法、改性手段及烧结工艺等3方面,归纳和分析了层状结构Ca_3Co_4O_9的研究进展,并对Ca_3Co_4O_9今后的研究发展提出一些建议。     

MnO_2掺杂量对BaCo_(0.05)Co_(0.1)Bi_(0.85)O_3厚膜NTCR电性能影响

以新型BaCo0.05Co0.1Bi0.85O3材料为基体,掺杂不同摩尔分数x(MnO2),在840℃下烧结4h制备了NTC厚膜电阻。借助XRD、SEM和直流阻温特性测试仪,研究x(MnO2)对电阻相组成、微结构及电性能的影响。结果表明:所得的NTC厚膜热敏电阻主要物相为具有钙钛矿结构的BaCo0.05Co0.1Bi0.85O3,且表面致密。当x(MnO2)超过5%时,有新相BaMnO3开始沿晶界析出,获得小尺寸晶粒;厚膜电阻的室温电阻率ρ25及B25/85值随x(MnO2)增加而升高;当x(MnO2)为10%时,ρ25从初始的13.5?·mm升高为810.0?·mm,B25/85值从600K升高到2049K。     

反应烧结压力对Bi2Te3半导体材料组织与性能的影响

以Bi和Te的单质为原料,用固相反应烧结法制备Bi2Te3P型半导体制冷材料.实验采用X射线衍射仪、莱卡光学显微镜分析压制工艺对材料组织性能的影响.实验结果表明:压力增加,塞贝克系数减少.压力较小时有BiTe存在,压力增加BiTe减少,Bi2Te3增加,300KN时基本为纯Bi2Te3     

CuO/CeO_2共掺杂Ba_(0.85)Ca_(0.15)Zr_(0.1)Ti_(0.9)O_3无铅压电陶瓷性能研究

采用固相反应法制备了CuO、CeO2共掺杂Ba0.85Ca0.15Zr0.1Ti0.9O3(BCZT)无铅压电陶瓷,研究了CuO的掺杂量对所制陶瓷晶体结构、压电及介电性能的影响。结果表明:CuO的加入,进一步降低了预先经0.05%(质量分数)CeO2掺杂的BCZT陶瓷的烧结温度;在1 250℃烧结时,仍可获得纯钙钛矿结构的BCZT陶瓷。当CuO掺杂量为质量分数0.2%时,所制BCZT陶瓷具有最佳的压电性能:d33=370 pC/N,tC约为93℃,tanδ=0.0147。     

Yb_2O_3/CoSb_3的机械合金化制备

以Co、Sb、Yb粉体为原料,采用机械合金化(MA)和热压烧结法(HIP)制备Yb2O3/CoSb3复合热电材料,并测试了该体系的电输运性质和热扩散系数。结果表明:球磨40 h后,Co、Sb发生合金化生成了CoSb3和CoSb2化合物相;球磨后的粉末在高纯Ar气氛(体积分数>99.99%)保护下经过50 MPa压强、530℃温度下热压烧结(HIP)2 h后合金内部主要由CoSb3相组成,同时合金内部有大量Yb2O3氧化物弥散掺杂,Yb2O3/CoSb3体系电阻率和热扩散系数随温度升高而降低。     

电场激活压力辅助烧结对(Bi2Te3)0.2(Sb2Te3)0.8热电材料微观结构及热电性能的影响

采用电场激活压力辅助烧结（FAPAS）技术制备了(Bi2Te3)0.2(Sb2Te3)0.8热电材料,采用无电场、低电场强度和高电场强度三种烧结方式作为对比实验,研究了烧结过程中施加电场强度对(Bi2Te3)0.2(Sb2Te3)0.8热电材料微观结构和热电性能的影响。研究结果表明,在烧结过程中施加电场,可明显提高(Bi2Te3)0.2(Sb2Te3)0.8热电材料的电导率和Seebeck系数,从而提高其综合电功率因子;而采用大电场强度烧结则会使(Bi2Te3)0.2(Sb2Te3)0.8材料出现层状结构择优取向,在电性能相对较高的情况下亦使其热导率明显减低,从而获得较高ZT值。     

铜掺杂量对钴酸钙热电性能的影响研究

采用sol-gel法制备了掺Cu的钴酸钙(Ca3Co4O9)热电材料,研究了Cu掺杂量对其物相、电导率σ、Seebeck系数S和功率因子P的影响。结果表明:随着Cu掺杂量的增加,试样中Ca3Co4O9的含量下降,但试样的电导率增加;试样的Seebeck系数和功率因子先增加后下降。试样(Ca0.90Cu0.10)3Co4O9在973 K时的功率因子最大,为15.3×10–4 W.m–1.K–2。     

Thermoelectric Properties of Ca3Co4O9/[Ca2(Co0.65Cu0.35)2O4]0.624CoO2 Composites

Ca₃Co₄O₉ is one of the most promising p-type thermoelectric materials because of its high dimensionless figure of merit ZT. However, polycrystalline Ca₃Co₄O₉ ceramics shows lower ZT value than that for single crystal Ca₃ Co₄O₉ due to its higher electrical resistivity ρ. Mikami et al. have reported that the addition of Ag to Ca₃Co₄O₉ ceramics could successfully reduce ρ and enhance the power factor. On the other hand, Ohtaki et al. reported that a composite structure could be highly effective to reduce κ for ZnO dually doped with Al and Ga. In this work, we tried to enhance the power factor and reduce κ by forming Ca₃Co₄O₉/[Ca₂(Co_0.65Cu_0.35)₂O₄]_0.624CoO₂ composite structure. As a result, the ZT value for Ca₃Co₄O₉/[Ca₂(Co_0.65Cu_0.35)₂O₄]_0.624CoO₂ composites reached 0.164 at 700 °C, which was 40 % higher than the value for Ca₃Co₄O₉.     

On the role of Bi2Sr2Ca1Cu2O8 and Bi2Sr2Cu1O6 on the weak links and critical currents in (Bi,Pb)2Sr2Ca2Cu2O10/Ag superconducting tapes

Silver-sheated (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀ (Bi2223) superconducting tapes with different Bi₂Sr₂CaCu₂O₈ (Bi2212) and Bi₂Sr₂Cu₁O₆ (Bi2201) concentrations, were prepared by using a two-step sintering processing and by varying cooling rates in the fabrication of the superconductors. The effect of residual Bi2212 and Bi2201 phases on weak links and critical currents of the Bi2223/Ag tapes was investigated. It was found that residual Bi2201 caused weak links at grain boundaries and limited the current-carrying capacity of the tapes. Comparatively, the residual Bi2212 phase had much less influence on both weak links and critical currents. Elimination of Bi2201 by sintering tapes at a low temperature in the final thermal cycle, or by cooling the tapes slowly, increased critical current by a factor of two. Flux pinning property was also improved by removing the residual Bi2201 phase.     

Bi2Te3热电材料改性研究及其进展

随着全球经济对高效、无污染能源转换的强劲需求,Bi2Te3半导体作为最优异的室温热电材料取得了长足稳步的发展。本文在简述Bi2Te3热电材料的结构和性能的基础上,重点介绍了掺杂、纳米化、掺杂与纳米化相结合的方法对Bi2Te3热电性能的影响,详细分析了其影响机制。结果表明,以上方法均能很大程度上提升Bi2Te3热电材料的热电性能,尤其是掺杂与纳米化相结合对热电性能的提高更为显著。最后,对Bi2Te3热电材料改性的研究方向进行了展望。     

Submillimeter transmission spectra of Sr2Ca2Cu4Oy

Transmission spectra of Sr₂Ca₂Cu₄O_y, which is a part of high T_c superconducting system Bi₂Sr₂Ca_n?1Cu_nO_z, and their temperature evolutions were investigated by monochromatic quasioptical submillimeter spectroscopy. Strong increase of high frequency conductivity in the range 80 to 350K was revealed. The obtained results were analyzed on basis of thermally activated carriers model.     

A Power-Generation Test for Oxide-Based Thermoelectric Modules Using p-Type Ca3Co4O9 and n-Type Ca0.9Nd0.1MnO3 Legs

Metal oxides are considered to be promising thermoelectric (TE) materials, especially for high-temperature power-generation applications, because they have many advantages such as low price, light weight, thermal stability, nontoxicity, and high oxidation resistance. For these reasons, oxide-based TE modules were fabricated using p-type pure Ca₃Co₄O₉ and n-type Ca_0.9Nd_0.1MnO₃ legs for power generation at temperatures in excess of 1000?K. This study involved the use of Ag sheets with a Ag paste as electrode materials and alumina plates as a substrate for the modules. The p-type pure Ca₃Co₄O₉ legs were manufactured by spark plasma sintering, and the n-type Ca_0.9Nd_0.1MnO₃ legs were sintered by a conventional process at atmospheric pressure. From a unicouple, a power density as high as 93.2?mW/cm² under a temperature condition of ??T?=?727?K (T _hot?=?1175?K) was obtained. This high power density is believed to be a result of the modified contact of the electrode (notch process) and the optimized material properties (the SPS process and a dopant effect) along with the high ??T obtained in this study (reduced thermal losses because of good packing of thermal insulation). Areas of concern for future research include the following: (1) the measured open-circuit voltage from the present unicouples was only 94.3% of the theoretical voltage, and (2) the internal resistance value was as high as 490% of the theoretical resistance.