CN114573348B - 一种提高Bi2Te3基热电材料热电性能的方法 - Google Patents
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Abstract
本发明涉及基热电材料技术领域,尤其涉及一种提高Bi2Te3基热电材料热电性能的方法。其步骤包括:用Te、Bi、Sb和Se单质粉体合成取向晶体;将取向晶体破碎成粉末,加入稀土元素Tb和金属元素Sn,粉碎得到Bi2Te3基P型赝三元热电材料合金粉体;后将合金粉体烘干,进行高压烧结成型;切割材料,退火,冷却。本发明中稀土掺杂可有效增加材料的点缺陷、晶界和位错,有效降低晶格热导率,同时辅以Sn的掺杂,可有效调节晶体的能带结构,增加费米能级附近的态密度,从而提升材料的热电性能,将材料的热电优值从0.5提高到1.25;本发明使用高压烧结技术与SPS技术相结合,高压烧结技术具有烧结效率高、烧结时间短、纳米晶均匀、压力变化连续可调。
Description
技术领域
本发明涉及热电材料技术领域,尤其涉及一种提高Bi2Te3基热电材料热电性能的方法。
背景技术
目前广泛应用的传统能源利用率十分有限,导致三分之二以上的工业余热得不到有效利用而浪费。而热电材料,因为固定内部的载流子电声输运特性,可以有效利用流失的工业余热。同时制备的热电器件还具无噪音、无污染、质量轻、性能稳定、服役寿命长、体积小等优点,在民用、航空、医疗等领域均有广阔的应用前景。
目前,热电材料的种类繁多,除了传统热电材料如室温热电材料Bi2Te3、中温热电材料PbTe、高温热电材料SiGe以外,多种高性能新型热电材料如方钴矿、SnSe、Half-Heuser基化合物以及Mg2Si1-xSnx均展示出了热电优势,得到了极大的开发。
然而,在众多的热电材料体系中,Bi2Te3基合金是室温附近性能最好的热电材料。其ZT值在室温附近为1左右,但随着温度升高,ZT值急剧降低,从而限制了Bi2Te3基合金在发电领域的应用。因此,进一步提高Bi2Te3基热电材料的热电性能,提高其应用价值、扩大其应用领域意义重大。除了通过新的制备技术来提高材料的热电性能外,掺杂也是提高材料热电性能的有效途径。稀土元素被认为是提高Bi2Te3基合金热电性能的重要掺杂元素,它可作为受主掺杂增加合金的载流子浓度,同时辅以Sn元素掺杂扩大材料带隙,使本征激发对材料热电性能的影响减弱。并结合高压烧结技术,可抑制晶粒长大,降低材料的晶格热导率,提高材料的机械性能,从而制备出可用于发电领域的高性能的P型Bi2Te3基热电材料。
发明内容
针对背景技术中存在的问题,提出一种提高Bi2Te3基热电材料热电性能的方法。本发明中稀土掺杂可有效增加材料的点缺陷、晶界和位错,有效降低晶格热导率,同时辅以Sn的掺杂,可有效调节晶体的能带结构,增加费米能级附近的态密度,从而提升材料的热电性能。本发明使用高压烧结技术与SPS技术相结合,高压烧结技术具有烧结效率高、烧结时间短、纳米晶均匀、压力变化连续可调。将材料的热电优值从0.5提高到1.25。
本发明提出一种提高Bi2Te3基热电材料热电性能的方法,步骤包括;
S1、用Te、Bi、Sb和Se单质粉体,按P型(Sb2Te3)0.73(Bi2Te3)0.24(Sb2Se3)0.03化学计量比配比,进行真空熔炼,将粉体合成取向晶体;
S2、将(Sb2Te3)0.73(Bi2Te3)0.24(Sb2Se3)0.03取向晶体破碎成粉末,加入稀土元素Tb和金属元素Sn,得混合物,将混合物机械球磨至粉碎,得到Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料合金粉体;
S3、将步骤S2所得的合金粉体烘干后,将合金粉末装入模具内,高压烧结成型,得高压烧结块体材料;
S4、将步骤S3所得的块体材料切割成条状,在真空条件下退火,后随炉冷却至室温,即得Tb和Sn双掺杂的Bi2Te3基P型赝三元热电材料。
优选的,在S1中,Te、Bi、Sb和Se单质粉体的纯度均为99.99%(质量分数),在温度为800℃时进行真空熔炼。
优选的,在S2中,将混合物机械球磨,粉碎至粒径为1mm-10mm,以石油醚为球磨介质,在转速为410r/min,球料比为10:1,球磨时间为50h的条件下,得到Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料合金粉体。
优选的,在S2中,稀土元素Tb和Sn的掺入量均为总摩尔质量的0.1%-1.5%。
优选的,在S3中,烘干温度设置为100℃,烘干后采用六面顶油压机进行高压烧结成型;高压烧结条件为:烧结压力6Gpa,烧结温度600K,恒温烧结10min,恒温恒压结束后在5min内冷却至室温。
优选的,在S4中,块体材料切割成4mm×4mm×10mm的条状;退火温度为600K,保温48h。
与现有技术相比,本发明具有如下有益的技术效果:
本发明制备工艺简单、易于操作、制备条件要求不高,可有效降低生产成本。机械合金化方法在机械球磨过程中将机械能转化为化学能,能够在室温下实现元素的化合,制备出合金超微粉体材料。高压烧结技术在实现样品良好烧结并获得高致密度的同时,可以有效地抑制晶粒长大。致密的微结构有利于获得良好的电学性能,而细小的晶粒可以使声子散射增强,降低材料的晶格热导率。同时结合退火处理,使材料内部的载流子迁移率大幅提升,缺陷减少,晶格完美度提升,缺陷对载流子的散射减少,从而提高材料的热电优值(ZT=1.25)。稀土Tb的掺杂可增加材料的载流子浓度,增强合金的散射能力,降低载流子的迁移率,从而使材料的电导率增大。同时,稀土Tb的掺杂使Bi2Te3基P型赝三元热电材料的样品晶胞体积增大,从而降低材料的热导率。同时辅以Sn元素的掺杂,一方面通过增加载流子的有效质量,使材料的能带结构变的更为复杂,从而提升了材料的Seebeck系数。另一方面,Sn元素的掺杂会抑制材料的本征激发和双级散射效应,引入大量的点缺陷,使材料的内部位错密度增加,晶格发生扭曲,从而增加多尺度声子散射,有效地降低晶格热导率,最终达到提高材料热电优值(ZT)的目的。
附图说明
图1为本发明中一种实施例所得Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料的载流子浓度(n)和迁移率(μ)图;
图2为本发明中一种实施例中T为350K时所得Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料的电导率图;
图3为本发明中一种实施例中T为350K时所得Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料的Seebeck系数图;
图4为本发明中一种实施例中T为350K时所得Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料功率因子(PF)图;
图5为本发明中一种实施例中T为350K时所得Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料的总热导率(k)图;
图6为本发明中一种实施例中T为350K时所得Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料热电优值(ZT)图。
图7为本发明中一种实施例中X为0.7%时所得Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料的电导率图;
图8为本发明中一种实施例中X为0.7%时所得Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料的Seebeck系数图。
具体实施方式
实施例一
本发明提出的一种提高Bi2Te3基热电材料热电性能的方法,步骤包括;
S1、用纯度均为99.99%(质量分数)的Te、Bi、Sb和Se单质粉体,按P型(Sb2Te3)0.73(Bi2Te3)0.24(Sb2Se3)0.03化学计量比配比,在温度为800℃时进行真空熔炼,将粉体合成取向晶体;Te、Bi、Sb和Se单质粉体的;
S2、将(Sb2Te3)0.73(Bi2Te3)0.24(Sb2Se3)0.03取向晶体破碎成粉末,加入稀土元素Tb和金属元素Sn,稀土元素Tb和Sn的掺入量分别为总摩尔质量的0.1%、0.4%、0.7%、1.0%、1.2%、1.5%,得混合物,将混合物机械球磨,粉碎至粒径为1mm-10mm,以石油醚为球磨介质,在转速为410r/min,球料比为10:1,球磨时间为50h的条件下,得到Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料合金粉体;
S3、将步骤S2所得的合金粉体烘干后,将合金粉末装入模具内,高压烧结成型,得高压烧结块体;烘干温度设置为100℃,烘干后采用六面顶油压机进行高压烧结成型;高压烧结条件为:烧结压力6Gpa,烧结温度分别为600K,恒温烧结10min,恒温恒压结束后在5min内冷却至室温。
S4、将步骤S3所得的块体切割成4mm×4mm×10mm的条状,在真空条件下退火,退火温度分别为300K、350K、400K、450K、500K、550K、600K,保温48h,后随炉冷却至室温,即得Tb和Sn双掺杂的Bi2Te3基P型赝三元热电材料。
结果分析:用霍尔效应实验仪测量仪对材料的室温霍尔系数进行测量,进而得到材料的载流子浓度n和迁移率μ,如图1所示。从图1可看出,未掺杂Tb和Sn的样品的载流子浓度n为2.4×1019cm-3,电子迁移率为270.45cm2V-1S-1,随着掺杂量的增加,样品的载流子浓度n随之增大,电子迁移率逐渐减小,当掺杂量为x=1.5%时,样品的载流子浓度达到最大为7.45×1019cm-3。载流子浓度的升高,一方面由于呈+3价的Tb掺杂Bi位后,Tb占据了范德瓦尔斯层的间隙位置,使得材料的载流子浓度升高。另一方面Sn的掺杂也使材料的载流子浓度增加。而迁移率的降低,是由于载流子浓度的增加增大了载流子间相互碰撞的几率,从而增大了载流子间的散射,导致材料的迁移率降低。
实施例二
本发明提出的一种提高Bi2Te3基热电材料热电性能的方法,步骤包括;
S1、用纯度均为99.99%(质量分数)的Te、Bi、Sb和Se单质粉体,按P型(Sb2Te3)0.73(Bi2Te3)0.24(Sb2Se3)0.03化学计量比配比,在温度为800℃时进行真空熔炼,将粉体合成取向晶体;Te、Bi、Sb和Se单质粉体的;
S2、将(Sb2Te3)0.73(Bi2Te3)0.24(Sb2Se3)0.03取向晶体破碎成粉末,加入稀土元素Tb和金属元素Sn,稀土元素Tb和Sn的掺入量分别为总摩尔质量的1.5%,得混合物,将混合物机械球磨,粉碎至粒径为1mm-10mm,以石油醚为球磨介质,在转速为410r/min,球料比为10:1,球磨时间为50h的条件下,得到Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料合金粉体;
S3、将步骤S2所得的合金粉体烘干后,将合金粉末装入模具内,高压烧结成型,得高压烧结块体;烘干温度设置为100℃,烘干后采用六面顶油压机进行高压烧结成型;高压烧结条件为:烧结压力6Gpa,烧结温度为600K,恒温烧结10min,恒温恒压结束后在5min内冷却至室温。
S4、将步骤S3所得的块体切割成4mm×4mm×10mm的条状,在真空条件下退火,退火温度分别为300K、350K、400K、450K、500K、550K、600K,保温48h,后随炉冷却至室温,即得Tb和Sn双掺杂的Bi2Te3基P型赝三元热电材料。
结果分析:
用热电特性评价装置对Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料进行电导率(σ)测量和Seebeck系数测量,分别如图2、图3所示,其中纵坐标σ和α表示电导率和Seebeck系数,横坐标X表示Tb和Sn掺杂浓度。当退火温度为350K时,掺杂后样品的电导率随着Tb和Sn的掺杂浓度的增加而增大,当掺杂量为1.5%时,室温下的电导率为10.94×104m·s-1,相比于为掺Tb和Sn样品室温电导率6.6×104m·s-1,提高了66%。说明载流子浓度和载流子迁移率的变化共同决定了电导率的大小,随着Tb和Sn的掺杂浓度的增加,载流子浓度升高,电子迁移率降低,使得电导率增大。而样品的Seebeck系数随的Tb和Sn掺杂浓度的增加而减小,这是由于Seebeck系数和散射因子成正比,与载流子浓度成反比,而载流子浓度的变化是影响Seebeck系数的主要因素,从而使样品的Seebeck系数减小。
用热电特性评价装置对Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料进行电导率(σ)测量和Seebeck系数测量,如图2、图3所示,其中纵坐标σ和α表示电导率和Seebeck系数,横坐标T表示温度。当Tb和Sn掺杂浓度为0.7%时,随着温度的升高,样品的电导率逐渐减小,而Seebeck系数呈先增加后减小的趋势。当温度为350K时,Seebeck系数达到最大值为255.41μV/K。这说明,样品经过退火处理后,样品的缺陷减少,增加了样品的晶界,晶格完美度提高,对载流子的散射作用增强,费米能级的态密度增强。因此随着温度的升高,样品的载流子浓度降低,从而导致样品的电导率减小,Seebeck系数减小。
根据图2和图3的测试结果,可换成Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料的功率因子(PF)。如图4所示,其中纵坐标PF表示功率因子,横坐标X表示掺杂浓度。掺杂后的样品均表现出较高的功率因子,最优值从3.97W/K-2提高到5.033W/K-2,展现出非常好的热电特性。
用热导率测试仪对Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料进行导热系数测量,如图5所示,其中纵坐标k表示热导率,横坐标X表示掺杂浓度。如图所示,当退火温度为350K时,样品的总热导率随着掺杂浓度的增加,表现为先减小后增大的趋势。当Tb和Sn的掺杂量为0.7%时,材料的热导率达到最低,为1.08w/mK,说明通过元素Tb和Sn的掺杂,引入了点缺陷,对短波声子产生强烈的散射作用,从而降低了热导率。
根据图4和图5的测量结果,可换算成Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料的无量纲热电优值(ZT值),如图6所示,其中纵坐标ZT表示热电优值,横坐标x表示掺杂浓度温度。掺杂后的样品热电优值明显提高,当掺杂浓度为0.7%时,最优值(ZT)从0.53584提高到1.25,因此具有很强的应用前景。
上面结合附图对本发明的实施方式作了详细说明,但是本发明并不限于此,在所属技术领域的技术人员所具备的知识范围内,在不脱离本发明宗旨的前提下还可以作出各种变化。
Claims (1)
1.一种提高Bi2Te3基热电材料热电性能的方法,其特征在于,步骤包括;
S1、用Te、Bi、Sb和Se单质粉体,按P型(Sb2Te3)0.73(Bi2Te3)0.24(Sb2Se3)0.03化学计量比配比,进行真空熔炼,将粉体合成取向晶体;Te、Bi、Sb和Se单质粉体的纯度均为99.99%,在温度为800℃时进行真空熔炼;
S2、将(Sb2Te3)0.73(Bi2Te3)0.24(Sb2Se3)0.03取向晶体破碎成粉末,加入稀土元素Tb和金属元素Sn,得混合物,将混合物机械球磨至粉碎,得到Tb和Sn共掺杂的Bi2Te3基P型赝三元热电材料合金粉体;粉体粒径为1mm-10mm,以石油醚为球磨介质,在转速为在转速为410r/min,球料比为10:1,球磨时间为50h;稀土元素Tb和Sn的掺入量均为总摩尔质量的0.1%-1.5%;
S3、将步骤S2所得的合金粉体烘干后,将合金粉末装入模具内,高压烧结成型,得高压烧结块体材料;烘干温度设置为100℃,烘干后采用六面顶油压机进行高压烧结成型;高压烧结条件为:烧结压力6Gpa,烧结温度600K,恒温烧结10min,恒温恒压结束后在5min内冷却至室温;
S4、将步骤S3所得的块体材料切割成条状,在真空条件下退火,后随炉冷却至室温,即得Tb和Sn双掺杂的Bi2Te3基P型赝三元热电材料;块体材料切割成4mm×4mm×10mm的条状;退火温度为600K,保温48h。
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