CN112079638A - 一种兼具高热电和力学性能的p型碲化铋基热电材料及其制备方法 - Google Patents
一种兼具高热电和力学性能的p型碲化铋基热电材料及其制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 114
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 41
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 39
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000002474 experimental method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 229910020073 MgB2 Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 238000007906 compression Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
一种兼具高热电和力学性能的p型碲化铋基热电材料及其制备方法，本发明涉及一种p型碲化铋基热电材料及其制备方法。本发明要解决现有p型碲化铋基热电材料力学性能差的问题。兼具高热电和力学性能的p型碲化铋基热电材料的化学通式为(MgB2)xBi0.4Sb1.6‑xTe3；方法：一、称取；二、制备铸锭；三、研磨并烧结。本发明用于兼具高热电和力学性能的p型碲化铋基热电材料及其制备。
Description
技术领域
本发明涉及一种p型碲化铋基热电材料及其制备方法。
背景技术
热电材料可以实现热能与电能之间的相互转换，依据塞贝克与帕尔贴效应，可分别制备成温差发电与固态制冷器件，具有无污染、无噪声、体积小、稳定性高、寿命长等优点，可广泛应用于余热回收、制冷、深空探测等领域。p型碲化铋基材料是目前唯一商业化应用的p-型热电材料，通过载流子调控和纳米化等手段，获得了高的低温热电性能。但是，碲化铋基材料晶体结构为六面体层状结构，层与层之间Te1-Te1的弱范德华键极易导致材料发生解理断裂，致使其力学性能差。传统商用铸锭，压缩强度低于50MPa，增加了材料的加工难度，使得生产过程中成品率低，浪费严重。因此，获得兼具高热电和力学性能的p型碲化铋基材料意义重大。
发明内容
本发明要解决现有p型碲化铋基热电材料力学性能差的问题，而提供一种兼具高热电和力学性能的p型碲化铋基热电材料及其制备方法。
一种兼具高热电和力学性能的p型碲化铋基热电材料的化学通式为(MgB2)xBi0.4Sb1.6-xTe3，0.005≤x≤0.015。
一种兼具高热电和力学性能的p型碲化铋基热电材料的制备方法，它是按照以下步骤进行的：
一、称取：
按照化学通式为(MgB2)xBi0.4Sb1.6-xTe3的化学计量比称取MgB2粉、Bi粉、Sb粉和Te粉，然后混合均匀，得到混合物；0.005≤x≤0.015；
二、制备铸锭：
将混合物置于涂碳石英管内，抽真空后封管，将封好的涂碳石英管置于高温马弗炉中，以升温速度为180℃/h～220℃/h，将马弗炉升温至750℃～850℃，并在温度为750℃～850℃的条件下，保温8h～10h，然后随炉冷却至室温，得到铸锭；
三、研磨并烧结：
将铸锭置于不锈钢球磨罐中，球磨2h～4h，得到细粉，将细粉置于石墨模具中，利用放电等离子烧结炉，在温度为380℃～420℃及压力为70MPa～90MPa的条件下，烧结3min～5min，即完成兼具高热电和力学性能的p型碲化铋基热电材料的制备方法；
所述的细粉粒径为50纳米～100纳米。
本发明的有益效果是：本发明公开了一种兼具高热电和力学性能的Bi0.4Sb1.6Te3基热电材料及其制备方法。采用极少量的MgB2掺杂，一方面，少量的Mg取代Bi0.4Sb1.6Te3中Bi或者Sb的位置，增加载流子浓度，延缓本征激发的出现，拓展材料的工作温度区间；另一方面，B的加入起到强化的作用，使得材料的压缩强度大幅度提高。MgB2掺杂在Bi0.4Sb1.6Te3中实现了受主掺杂优化载流子浓度和固溶强化的协同作用，同时获得了高的热电和力学性能。在冷端温度为305K、热端温度为575K及腿长为2mm的条件下，能量转换效率和输出功率密度分别达到了9.8％和2.43Wcm-2，接近目前最高水平。同时，室温压缩强度从166MPa提高到了239MPa，改善了材料的力学性能，进一步提高了Bi0.4Sb1.6Te3材料商用前景。
本发明用于一种兼具高热电和力学性能的p型碲化铋基热电材料及其制备方法。
附图说明
图1为电导率对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料；
图2为塞贝克系数对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料；
图3为功率因子对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料；
图4为热导率对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料；
图5为热电优值对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料；
图6为在冷端温度为305K、热端温度为575K及腿长为2mm的条件下，输出功率密度对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料；
图7为在冷端温度为305K、热端温度为575K及腿长为2mm的条件下，转换效率对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料；
图8为压缩强度对比图，a为对比实验一制备的Bi0.4Sb1.6Te3热电材料，b为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，c为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料。
具体实施方式
本发明技术方案不局限于以下所列举的具体实施方式，还包括各具体实施方式之间的任意组合。
具体实施方式一：本实施方式一种兼具高热电和力学性能的p型碲化铋基热电材料的化学通式为(MgB2)xBi0.4Sb1.6-xTe3，0.005≤x≤0.015。
本实施方式的有益效果是：本实施方式公开了一种兼具高热电和力学性能的Bi0.4Sb1.6Te3基热电材料及其制备方法。采用极少量的MgB2掺杂，一方面，少量的Mg取代Bi0.4Sb1.6Te3中Bi或者Sb的位置，增加载流子浓度，延缓本征激发的出现，拓展材料的工作温度区间；另一方面，B的加入起到强化的作用，使得材料的压缩强度大幅度提高。MgB2掺杂在Bi0.4Sb1.6Te3中实现了受主掺杂优化载流子浓度和固溶强化的协同作用，同时获得了高的热电和力学性能。在冷端温度为305K、热端温度为575K及腿长为2mm的条件下，能量转换效率和输出功率密度分别达到了9.8％和2.43Wcm-2，接近目前最高水平。同时，室温压缩强度从166MPa提高到了239MPa，改善了材料的力学性能，进一步提高了Bi0.4Sb1.6Te3材料商用前景。
具体实施方式二：本实施方式与具体实施方式一不同的是：所述的兼具高热电和力学性能的p型碲化铋基热电材料的化学通式为(MgB2)xBi0.4Sb1.6-xTe3，0.005≤x≤0.01。其它与具体实施方式一相同。
具体实施方式三：本实施方式与具体实施方式一或二之一不同的是：所述的兼具高热电和力学性能的p型碲化铋基热电材料的化学通式为(MgB2)xBi0.4Sb1.6-xTe3，x＝0.01。其它与具体实施方式一或二相同。
具体实施方式四：本实施方式一种兼具高热电和力学性能的p型碲化铋基热电材料的制备方法，它是按照以下步骤进行的：
一、称取：
按照化学通式为(MgB2)xBi0.4Sb1.6-xTe3的化学计量比称取MgB2粉、Bi粉、Sb粉和Te粉，然后混合均匀，得到混合物；0.005≤x≤0.015；
二、制备铸锭：
将混合物置于涂碳石英管内，抽真空后封管，将封好的涂碳石英管置于高温马弗炉中，以升温速度为180℃/h～220℃/h，将马弗炉升温至750℃～850℃，并在温度为750℃～850℃的条件下，保温8h～10h，然后随炉冷却至室温，得到铸锭；
三、研磨并烧结：
将铸锭置于不锈钢球磨罐中，球磨2h～4h，得到细粉，将细粉置于石墨模具中，利用放电等离子烧结炉，在温度为380℃～420℃及压力为70MPa～90MPa的条件下，烧结3min～5min，即完成兼具高热电和力学性能的p型碲化铋基热电材料的制备方法；
所述的细粉粒径为50纳米～100纳米。
具体实施方式五：本实施方式与具体实施方式四不同的是：步骤三中将铸锭置于不锈钢球磨罐中，利用SPEX-8000M型高能球磨机球磨2h～4h，得到细粉。其它与具体实施方式四相同。
具体实施方式六：本实施方式与具体实施方式四或五之一不同的是：步骤一中0.005≤x≤0.01。其它与具体实施方式四或五相同。
具体实施方式七：本实施方式与具体实施方式四至六之一不同的是：步骤一中x＝0.01。其它与具体实施方式四至六之一相同。
具体实施方式八：本实施方式与具体实施方式四至七之一不同的是：步骤二中以升温速度为200℃/h～220℃/h，将马弗炉升温至800℃～850℃。其它与具体实施方式四至七相同。
具体实施方式九：本实施方式与具体实施方式四至八之一不同的是：步骤二中在温度为800℃～850℃的条件下，保温9h～10h。其它与具体实施方式四至八相同。
具体实施方式十：本实施方式与具体实施方式四至九之一不同的是：步骤三中在温度为400℃～420℃及压力为80MPa～90MPa的条件下，烧结4min～5min。其它与具体实施方式四至九相同。
采用以下实施例验证本发明的有益效果：
实施例一：
一种兼具高热电和力学性能的p型碲化铋基热电材料，兼具高热电和力学性能的p型碲化铋基热电材料的化学通式为(MgB2)xBi0.4Sb1.6-xTe3，x＝0.01；
上述兼具高热电和力学性能的p型碲化铋基热电材料，它是按照以下步骤进行的：
一、称取：
按照化学通式为(MgB2)xBi0.4Sb1.6-xTe3的化学计量比称取MgB2粉、Bi粉、Sb粉和Te粉，然后混合均匀，得到混合物；x＝0.01；
二、制备铸锭：
将混合物置于涂碳石英管内，抽真空后封管，将封好的涂碳石英管置于高温马弗炉中，以升温速度为200℃/h，将马弗炉升温至800℃，并在温度为800℃的条件下，保温10h，然后随炉冷却至室温，得到铸锭；
三、研磨并烧结：
将铸锭置于不锈钢球磨罐中，利用SPEX-8000M型高能球磨机球磨2h，得到细粉，将细粉置于石墨模具中，利用放电等离子烧结炉，在温度为400℃及压力为80MPa的条件下，烧结5min，得到MgB2掺杂Bi0.4Sb1.6Te3热电材料，即完成兼具高热电和力学性能的p型碲化铋基热电材料的制备方法；
所述的细粉粒径为50纳米。
实施例二：本实施例与实施例一不同的是：步骤一中所述的x＝0.005。其它与实施例一相同。
对比实验一：本实施例与实施例一不同的是：步骤一中所述的x＝0；步骤三中得到Bi0.4Sb1.6Te3热电材料，其它与实施例一相同。
图1为电导率对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料；
图2为塞贝克系数对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料；
图3为功率因子对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料。
由图1至3可知，MgB2掺杂后Bi0.4Sb1.6Te3的电导率大幅的增加，实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料室温电导率增加至125.9×103Sm-1。相应地，塞贝克系数降低，实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料室温塞贝克系数降低至184.0μVK-1。最终，材料的功率因子明显增加。尤其是在573K，功率因子从5.18μWcm-1K-2提高到了实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料的13.1μWcm-1K-2。
图4为热导率对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料。
由图4可知，实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料室温热导率增加至1.17Wm-1K-1；但在573K时，MgB2掺杂使实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料热导率降低至1.53Wm-1K-1，说明MgB2掺杂可以降低Bi0.4Sb1.6Te3材料较高温度区间的热导率。
图5为热电优值对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料。
由图5可知，MgB2掺杂虽然没有提高材料的ZT值峰值，但使得材料的ZT值峰值对应温度从室温(300K)提高到了400K，拓展了材料的最佳使用温度区间。
图6为在冷端温度为305K、热端温度为575K及腿长为2mm的条件下，输出功率密度对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料；
图7为在冷端温度为305K、热端温度为575K及腿长为2mm的条件下，转换效率对比图，1为对比实验一制备的Bi0.4Sb1.6Te3热电材料，2为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，3为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料。
由图6及7可知，实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料的输出功率密度在573K时达到2.43Wcm-2，较未掺杂Bi0.4Sb1.6Te3提高了47.5％；实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料的转换效率达到9.88％，较未掺杂Bi0.4Sb1.6Te3提高了21％。
在室温条件下进行压缩试验，压缩样品尺寸均按照国标GB/T 10623执行，尺寸为2mm×2mm×5.5mm。图8为压缩强度对比图，a为对比实验一制备的Bi0.4Sb1.6Te3热电材料，b为实施例一制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料，c为实施例二制备的MgB2掺杂Bi0.4Sb1.6Te3热电材料。由图8可知，MgB2掺杂后，压缩强度从166MPa提到到了239MPa，提到了约44％。
Claims (10)
1.一种兼具高热电和力学性能的p型碲化铋基热电材料，其特征在于兼具高热电和力学性能的p型碲化铋基热电材料的化学通式为(MgB2)xBi0.4Sb1.6-xTe3，0.005≤x≤0.015。
2.根据权利要求1所述的一种兼具高热电和力学性能的p型碲化铋基热电材料，其特征在于所述的兼具高热电和力学性能的p型碲化铋基热电材料的化学通式为(MgB2)xBi0.4Sb1.6-xTe3，0.005≤x≤0.01。
3.根据权利要求1所述的一种兼具高热电和力学性能的p型碲化铋基热电材料，其特征在于所述的兼具高热电和力学性能的p型碲化铋基热电材料的化学通式为(MgB2)xBi0.4Sb1.6-xTe3，x＝0.01。
4.如权利要求1所述的一种兼具高热电和力学性能的p型碲化铋基热电材料的制备方法，其特征在于它是按照以下步骤进行的：
一、称取：
按照化学通式为(MgB2)xBi0.4Sb1.6-xTe3的化学计量比称取MgB2粉、Bi粉、Sb粉和Te粉，然后混合均匀，得到混合物；0.005≤x≤0.015；
二、制备铸锭：
将混合物置于涂碳石英管内，抽真空后封管，将封好的涂碳石英管置于高温马弗炉中，以升温速度为180℃/h～220℃/h，将马弗炉升温至750℃～850℃，并在温度为750℃～850℃的条件下，保温8h～10h，然后随炉冷却至室温，得到铸锭；
三、研磨并烧结：
将铸锭置于不锈钢球磨罐中，球磨2h～4h，得到细粉，将细粉置于石墨模具中，利用放电等离子烧结炉，在温度为380℃～420℃及压力为70MPa～90MPa的条件下，烧结3min～5min，即完成兼具高热电和力学性能的p型碲化铋基热电材料的制备方法；
所述的细粉粒径为50纳米～100纳米。
5.根据权利要求4所述的一种兼具高热电和力学性能的p型碲化铋基热电材料的制备方法，其特征在于步骤三中将铸锭置于不锈钢球磨罐中，利用SPEX-8000M型高能球磨机球磨2h～4h，得到细粉。
6.根据权利要求4所述的一种兼具高热电和力学性能的p型碲化铋基热电材料的制备方法，其特征在于步骤一中0.005≤x≤0.01。
7.根据权利要求4所述的一种兼具高热电和力学性能的p型碲化铋基热电材料的制备方法，其特征在于步骤一中x＝0.01。
8.根据权利要求4所述的一种兼具高热电和力学性能的p型碲化铋基热电材料的制备方法，其特征在于步骤二中以升温速度为200℃/h～220℃/h，将马弗炉升温至800℃～850℃。
9.根据权利要求4所述的一种兼具高热电和力学性能的p型碲化铋基热电材料的制备方法，其特征在于步骤二中在温度为800℃～850℃的条件下，保温9h～10h。
10.根据权利要求4所述的一种兼具高热电和力学性能的p型碲化铋基热电材料的制备方法，其特征在于步骤三中在温度为400℃～420℃及压力为80MPa～90MPa的条件下，烧结4min～5min。
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| CN113773083B (zh) * | 2021-09-13 | 2022-10-04 | 哈尔滨工业大学 | 一种兼具高强度和高热电性能的碲化铋基材料及其制备方法 |
| CN115322004A (zh) * | 2022-08-22 | 2022-11-11 | 哈尔滨工业大学（深圳） | 一种兼具高热电和力学性能的碲化铋基热电材料及其制备方法 |
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