CN112216783B - 一种Ga-Ti掺杂ZnO块体热电材料的制备方法 - Google Patents
一种Ga-Ti掺杂ZnO块体热电材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种Ga‑Ti掺杂ZnO块体热电材料的制备方法，具体步骤如下：首先按配比称量ZnO、Ga2O3、TiO2粉末，并进行球磨，得到混合粉末；混合粉末过筛后，将所得粉末等静压成型；最后将成型的坯体进行固相烧结，烧结后随炉冷却得到Ga‑Ti掺杂ZnO块体热电材料。本发明工艺易于操作，制备的热电材料致密度高，并满足器件应用中对材料功率因子的要求，为掺杂ZnO热电材料的制备提供了一种简便高效的方法。
Description
技术领域
本发明属于能源材料技术领域，具体涉及一种制备Ga-Ti掺杂ZnO块体热电材料的方法。
背景技术
随着工业化的高速发展，能源与环境问题已经成为人类社会的重要问题之一。热电材料是一种能直接实现热能和电能相互转化的功能材料，在国防、航空航天、微电子等领域，特别是在温差发电和热电致冷等方面具有广泛的应用前景。
ZnO热电材料是一类高温热电材料，与传统高性能热电材料碲化铋、碲化铅相比，具有原料廉价易得、低毒、高温稳定性好等优点，但因其晶体结构简单，导致其电导率较低，无法获得较优异的热电性能。与纯ZnO相比，掺杂后的ZnO具有更低的电阻率和更好的稳定性。目前常用来掺杂的元素有Al、Ga、In、Sb、Si，其中Al掺杂性能最优，但是根据已报道的ZnO-Al2O3体系相图，Al2O3在ZnO中固溶度非常低，严重限制了Al掺杂对ZnO热电性能的提升。
Ga作为第三主族与Al性质相近的金属元素，被认为是一种有效的n型掺杂剂。Ga3+的半径比Al3+更接近Zn2+，同时Ga-O的键长比Al-O更接近Zn-O，所以在Zn位点上掺杂Ga会引入较小的晶体结构畸变。Ti是一种高价态金属，主要以Ti4+形式存在，与Al3+，Ga3+相比，可以多提供一个自由电子，从而提高材料的导电性能。因此Ga、Ti元素被认为是最有前景的掺杂元素。
除单一掺杂外，为了进一步提高材料的热电性能，往往对ZnO进行不同元素的共掺杂。目前已有通过热压烧结法、放电等离子烧结法、磁控溅射法等制备了掺杂ZnO热电材料，然而上述方法往往操作困难、设备价格昂贵、制备周期长，难以实现产业化生产。本发明提供了一种低成本、简单制备Ga-Ti掺杂ZnO块体热电材料的方法，制备的材料满足器件应用中对功率因子的要求。
发明内容
本发明的目的是提供一种制备Ga-Ti掺杂ZnO块体热电材料的方法，解决了现有的材料无法满足器件应用中对功率因子的数量级要求的问题。
本发明所采用的技术方案是，一种制备Ga-Ti掺杂ZnO块体热电材料的方法，具体步骤如下：
步骤1，按配比称量ZnO、Ga2O3、TiO2粉末，并进行球磨，得到混合粉末；
步骤2，将步骤1所得混合粉末过筛；
步骤3，将步骤2所得粉末等静压成型；
步骤4，将步骤3成型的坯体进行固相烧结，烧结后随炉冷却得到Ga-Ti掺杂ZnO块体热电材料。
本发明的特征还在于，
步骤1中按照分子式Zn0.998-x-yGaxTiyO，其中0≤x≤0.01，0≤y≤0.01，称量ZnO、Ga2O3、TiO2粉末。
步骤2中先将混合粉末置于100目筛过筛，再经过200目筛过筛，取100-200目之间粉末晾干备用
步骤3的成型过程：先将粉末预压成型，成型压力为5～10MPa、保压时间为30～90s；随后将预成型坯体等静压成型，成型压力为20～25MPa，保压时间为5～10min。
步骤3等静压成型时，坯体应处于真空状态。
步骤4的烧结温度为900～1300℃，保温时间为10～15h，烧结完成后以2℃/min的速率降至室温。
步骤1中球磨时，利用乙醇进行湿法球磨，球料质量比为5:1，球磨时间为8～10h。
本发明的有益效果是，本制备方法以等静压成型与传统固相烧结相结合，通过等静压成型获得各向均匀压实的坯体，均匀性好，不易分层，同时不需要加入粘合剂，减少了试样中引入杂质的机率，降低试样烧结后的气孔率，最终有益于提高试样的电学及热电性能。通过长时间的湿法球磨，使不同粉末混合均匀，在烧结时不同原子之间相互接触更加充分，从而保证了扩散均匀，进一步提高了试样的致密度。本发明工艺易于操作，制备的块体热电材材料满足器件应用中对功率因子的要求，并且生产成本低，便于工业化批量生产。
附图说明
图1本发明实施例1中Zn0.998Ga0.002O制备的掺杂ZnO块体热电材料的SEM图像；
图2本发明实施例1中Zn0.998Ga0.002O制备掺杂ZnO块体热电材料的功率因子随温度的变化图。
具体实施方式
下面结合具体实施方式对本发明进行详细说明。
本发明一种固相烧结制备Ga-Ti掺杂ZnO块体热电材料的方法，具体步骤如下：
步骤1，按配比称量ZnO、Ga2O3、TiO2粉末，并进行球磨，得到混合粉末；
步骤1中按照分子式Zn0.998-x-yGaxTiyO(0≤x≤0.01，0≤y≤0.01)称量ZnO、Ga2O3、TiO2粉末；球磨时，利用乙醇进行湿法球磨，球料质量比为5:1，球磨时间为8～10h。
步骤2，将步骤1所得混合粉末过筛；
步骤2中先将混合粉末置于100目筛过筛，再经过200目筛过筛，取100-200目之间粉末晾干备用；
步骤3，将步骤2所得粉末等静压成型；
步骤3的成型过程的具体过程：先将混合粉末预压成型，成型压力为5～10MPa、保压时间为30～90s；随后将预压成型的坯体等静压成型，等静压过程中，坯体处于真空状态，成型压力为20～25MPa，保压时间为5～10min。
步骤4，将步骤3成型的坯体固相烧结，烧结后随炉冷却得到Ga-Ti掺杂ZnO块体热电材料。
步骤4中的烧结温度为900～1300℃，保温10～15h，烧结完成后以2℃/min的速率降至室温。
实施例1
步骤1，根据分子式Zn0.998Ga0.002O按配比称量9.978g的ZnO、0.022g的Ga2O3粉末，利用乙醇进行湿法球磨，球料质量比为5:1，球磨时间为8h后得到混合粉末；
步骤2，步骤1中混合粉末先后置于100、200目筛过筛两遍，取100-200目之间粉末晾干备用；
步骤3，取步骤2混合粉末，在台式压力机上将粉末压制成型，成型压力为5MPa、保压时间为30s；随后将处于真空体系的坯体在等静压机上进一步成型，成型压力为22MPa，保压时间为5min。
步骤4，将步骤3成型的坯体在1200℃，保温10进行烧结，随后随炉冷却，得到Ga掺杂ZnO块体热电材料。
实施例1所得材料的致密度为97.12％，室温电阻率为3.31×10-3Ω·cm，在800K时功率因子为2.29×10-4W·m-1·K-2，该结果优于未掺杂ZnO。
实施例2
步骤1，根据分子式Zn0.998Ti0.002O按配比称量9.942g的ZnO、0.058g的TiO2粉末，利用乙醇进行湿法球磨，球料质量比为5:1，球磨时间为8h后得到混合粉末；
步骤2，步骤1中混合粉末先后置于100、200目筛过筛两遍，取100-200目之间粉末晾干备用；
步骤3，取步骤2混合粉末，在台式压力机上将粉末压制成型，成型压力为5MPa、保压时间为30s；随后将处于真空体系的坯体在等静压机上进一步成型，成型压力为22MPa，保压时间为5min。
步骤4，将步骤3成型的坯体在1200℃，保温10h进行烧结，随后随炉冷却，得到Ti掺杂ZnO块体热电材料。
实施例2所得材料的致密度为98.55％，室温电阻率为7.62×10-2Ω·cm，在800K时功率因子为3.91×10-5W·m-1·K-2，该结果优于未掺杂ZnO。
实施例3
步骤1，根据分子式Zn0.99Ti0.01O按配比称量9.893g的ZnO、0.107g的TiO2粉末，利用乙醇进行湿法球磨，球料质量比为5:1，球磨时间为8h后得到混合粉末；
步骤2，步骤1中混合粉末先后置于100、200目筛过筛两遍，取100-200目之间粉末晾干备用；
步骤3，取步骤2混合粉末，在台式压力机上将粉末压制成型，成型压力为5MPa、保压时间为30s；随后将处于真空体系的坯体在等静压机上进一步成型，成型压力为22MPa，保压时间为5min。
步骤4，将步骤3成型的坯体在1200℃，保温10h进行烧结，随后随炉冷却，得到Ga-Ti掺杂ZnO块体热电材料。
实施例3所得材料的致密度为99.16％，室温电阻率为9.76×10-2Ω·cm，在800K时功率因子为2.05×10-5W·m-1·K-2，该结果优于未掺杂ZnO。
实施例4
步骤1，根据分子式Zn0.997Ga0.002Ti0.001O按配比称量9.949g的ZnO、0.022g的Ga2O3、0.029g的TiO2，利用乙醇进行湿法球磨，球料质量比为5:1，球磨时间为10h后得到混合粉末；
步骤2，步骤1中混合粉末先后置于100、200目筛过筛两遍，取100-200目之间粉末晾干备用；
步骤3，取步骤2混合粉末，在台式压力机上将粉末压制成型，成型压力为10MPa、保压时间为60s；随后将处于真空体系的坯体在等静压机上进一步成型，成型压力为25MPa，保压时间为10min。
步骤4，将步骤3成型的坯体在900℃，保温10h进行烧结，随后随炉冷却，得到Ga-Ti掺杂ZnO块体热电材料。
实施例4所得材料的致密度为98.38％，室温电阻率为3.44×10-4Ω·cm，在800K时功率因子为2.07×10-4W·m-1·K-2，该结果优于未掺杂ZnO。
实施例5
步骤1，根据分子式Zn0.995Ga0.002Ti0.003O按配比分别称量9.892g的ZnO、0.021g的Ga2O3、0.087g的TiO2，利用乙醇进行湿法球磨，球料质量比为5:1，球磨时间为9h后得到混合粉末；
步骤2，步骤1中混合粉末先后置于100、200目筛过筛两遍，取100-200目之间粉末晾干备用；
步骤3，取步骤2混合粉末，在台式压力机上将粉末压制成型，成型压力为7MPa、保压时间为90s；随后将处于真空体系的坯体在等静压机上进一步成型，成型压力为25MPa，保压时间为8min。
步骤4，将步骤3成型的坯体在1300℃，保温15h进行烧结，随后随炉冷却，得到Ga-Ti掺杂ZnO块体热电材料。
实施例5所得材料的致密度为98.58％，室温电阻率为8.79×10-3Ω·cm，在800K时功率因子为1.5×10-4W·m-1·K-2，该结果优于未掺杂ZnO。
本发明以ZnO、Ga2O3、TiO2为原料，按照分子式Zn0.998-x-yGaxTiyO(0≤x≤0.01，0≤y≤0.01)配置粉末，利用乙醇对配置粉末进行湿法球磨后，过筛取100-200目粉末预压成型，随后等静压成型，最后将成型坯体在900～1300℃下，固相烧结10～15h，得到Ga-Ti掺杂ZnO块体材料。本发明制备Ga-Ti掺杂ZnO块体热电材料，以等静压成型与传统固相烧结相结合。等静压成型技术减少了试样中引入杂质的机率，降低试样烧结后的气孔率，保证了试样具有高的致密度，最终提高试样的热电性能。
本发明工艺易于操作，生产成本低，便于工业化批量生产，制备的块体热电材料满足器件应用中对功率因子的要求。同时，本发明制备方法简单、制备过程中没有用到其他化学试剂，满足了现代工业制造绿色、环保的要求。
Claims (6)
1.一种Ga-Ti掺杂ZnO块体热电材料的制备方法，其特征在于，具体步骤如下：
步骤1，按配比称量ZnO、Ga2O3、TiO2粉末，并进行球磨，得到混合粉末；所述步骤1中按照分子式Zn0.998-x-yGaxTiyO，其中0＜x≤0.01，0＜y≤0.01，称量ZnO、Ga2O3、TiO2粉末；
步骤2，将步骤1所得混合粉末过筛；
步骤3，将步骤2所得粉末等静压成型；
步骤4，将步骤3成型的坯体进行固相烧结，烧结后随炉冷却得到Ga-Ti掺杂ZnO块体热电材料。
2.根据权利要求1所述的一种Ga-Ti掺杂ZnO块体热电材料的制备方法，其特征在于，所述步骤2中先将混合粉末置于100目筛过筛，再经过200目筛过筛，取100-200目之间粉末晾干备用。
3.根据权利要求1所述的一种Ga-Ti掺杂ZnO块体热电材料的制备方法，其特征在于，所述步骤3的成型过程：先将粉末预压成型，成型压力为5~10MPa、保压时间为30~90s；随后将预成型坯体等静压成型，成型压力为20~25MPa，保压时间为5~10min。
4.根据权利要求1所述的一种Ga-Ti掺杂ZnO块体热电材料的制备方法，其特征在于，所述步骤3等静压成型时，坯体应处于真空状态。
5.根据权利要求1所述的一种Ga-Ti掺杂ZnO块体热电材料的制备方法，其特征在于，所述步骤4的烧结温度为900~1300℃，保温时间为10~15h，烧结完成后以2℃/min的速率降至室温。
6.根据权利要求1所述的一种Ga-Ti掺杂ZnO块体热电材料的制备方法，其特征在于，所述步骤1中球磨时，利用乙醇进行湿法球磨，球料质量比为5:1，球磨时间为8~10h。
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