CN110640138B - 一种ZrNiSn基Half-Heusler热电材料及其制备和调控反位缺陷的方法 - Google Patents
一种ZrNiSn基Half-Heusler热电材料及其制备和调控反位缺陷的方法 Download PDFInfo
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Abstract
本发明提供一种ZrNiSn基Half‑Heusler热电材料及其制备和调控反位缺陷的方法,ZrNiSn基Half‑Heusler热电材料的制备和调控反位缺陷的方法包括以下步骤:在氩气氛围或者密闭无氧环境中按照原子比1:1:1将Zr、Ni、Sn混合,将混合物料置于磁悬浮熔炼炉中熔炼得到铸锭,将铸锭研磨后干燥获得粉体,采用放电等离子体烧结技术将粉体烧结后至于真空容器中,热处理后淬火得到ZrNiSn基Half‑Heusler热电材料。本发明所述方法流程短、步骤少、易控制,能成功的制备出具有反位缺陷的ZrNiSn单相Half‑Heusler热电材料。
Description
技术领域
本发明涉及热电材料技术,尤其涉及一种ZrNiSn基Half-Heusler热电材料及其制备和调控反位缺陷的方法。
背景技术
热电发电技术在特种电源、绿色能源、环境能量收集与工业余热发电等领域具有重要的应用价值。近年来,热电材料的热电优值ZT不断获得突破,相应的热电器件应用技术的也得到了极大的发展。热电材料是一种可以直接将热能转换为电能的有效能源材料,具有较高稳定性及简单结构等特点,但是低的能效限制了它的应用。因此,如何有效提高热电材料的效率是当下一个研究热点。近年来,具有半导体特征或塞贝克效应的Half-Heusler(半哈斯勒)合金在温差发电领域表现出很好的应用前景,可作为一种典型的中高温热电材料。
热电材料的性能主要取决于其热电优值ZT,ZT值越大,其热电转换效率越高。热电优值定义为ZT=α2σT/κ,其中,α为塞贝克(Seebeck)系数,σ为电导率,α2σ也可定义为功率因子PF,T为绝对温度,κ为总的热导率,包括晶格(声子)热导率κl和电子热导率κe(κ=κl+κe)。然而,由于这些热电参数(Seebeck系数α、电导率σ和电子热导率κe)对载流子浓度n具有较强的依赖性,彼此相互耦合,即通过调节载流子浓度n获得高的电导率σ往往会导致低的Seebeck系数α和高的电子热导率κe。因此,如何有效提高ZT值一直是困扰学术界的难题。
Half-Heusler化合物由于具有良好的高温化学和热稳定性、优异的机械性能以及较高的高温热电优值,因此被认为是具有大规模商业化生产和应用的潜在热电材料。然而由于ZrNiSn基Half-Heusler化合物的热电性能对制备工艺较为敏感,不同的制备工艺容易使得材料微结构及原子无序度产生差异。由于Zr和Sn的原子半径相近,因此该缺陷容易在高温制备过程中原位生成,并通过退火进行回复。当Zr/Sn反位缺陷含量越高时,ZrNiSn热电材料由半导体特性转变为半金属特性。然而,早期的制备条件很难通过直接熔炼得到单相的样品,结构缺陷很难得到可靠的结果。
发明内容
本发明的目的在于,针对目前热电材料无法有效提高ZT值的问题,提出一种ZrNiSn基Half-Heusler热电材料的制备和调控反位缺陷的方法,该方法流程短、步骤少、易控制,能成功的制备出具有反位缺陷的ZrNiSn单相Half-Heusler热电材料。
为实现上述目的,本发明采用的技术方案是:一种ZrNiSn基Half-Heusler热电材料的制备和调控反位缺陷的方法,包括以下步骤:
在氩气氛围或者密闭无氧环境中按照原子比1:1:1将Zr、Ni、Sn混合,将混合物料置于磁悬浮熔炼炉中熔炼得到铸锭,将铸锭研磨后干燥获得粉体,采用放电等离子体烧结技术将粉体烧结后至于真空容器中,热处理后淬火得到ZrNiSn基Half-Heusler热电材料。
进一步地,ZrNiSn基Half-Heusler热电材料的制备和调控反位缺陷的方法,包括以下步骤:
(1)为防止氧化,在氩气氛围或者密闭无氧环境中按照原子比为1:1:1将Zr、Ni、Sn混合;
(2)将混合物料置于磁悬浮熔炼炉中熔炼,熔炼在氩气保护氛围下进行,将混合物料升温至1600~1800℃后保温1~5min得到铸锭,优选的升温至1650~1750℃后保温3~5min得到铸锭;
(3)将铸锭球磨至0.5-2μm,后自然干燥获得粉体;
(4)采用放电等离子体烧结技术将粉体进行烧结,烧结温度为800-1000℃,烧结压力为80-100MPa,保温时间为5-20min;优选的烧结温度为900-1000℃,烧结压力为80-100MPa,保温时间为10-20min;
(5)将烧结后的粉体置于真空容器中;
(6)将装有粉体的真空容器置于箱式高温烧结炉中进行长时间扩散退火处理;退火温度为800-1100℃、保温时间为12-36h;优选的退火温度为900-1000℃、保温时间为24-36h
(7)将保温后的装有试样的真空容器进行快速淬火处理得到ZrNiSn基Half-Heusler热电材料,降温速率为200-300℃/min。
进一步地,所述Zr、Ni、Sn纯度≥99.9%。
进一步地,所述Zr、Ni、Sn选取直径×长度为1×2mm~2×5mm的小颗粒。
进一步地,步骤(2)所述熔炼为3-6次,以保证熔炼后组织的均匀性。
进一步地,步骤(2)所述氩气保护氛围压力为104-105Pa。
进一步地,步骤(3)所述球磨:首先用研钵将铸锭粗磨成粒径0.1-1mm的粉体;然后在氩气氛围下进行湿法球磨。球磨介质为无水乙醇,球料比为10:1-20:1,转速为:200-600r/min,球磨时间为5-20h。
进一步地,步骤(3)所述干燥:在氩气氛围或者密闭无氧环境中将抽滤后的粉体进行12-48h的自然干燥处理。
进一步地,步骤(5)所述真空容器的真空度≤5×10-3Pa。所述真空容器包括但不限于直径15-30mm的石英玻璃管。
进一步地,步骤(7)淬火的淬火介质为水。
本发明的另一个目的还公开了一种ZrNiSn基Half-Heusler热电材料,采用上述方法制备而成。
本发明一种ZrNiSn基Half-Heusler热电材料及其制备和调控反位缺陷的方法,与现有技术相比较具有以下优点:
本发明以ZrNiSn合金为研究目标,利用磁悬浮熔炼结合放电等离子体烧结工艺制备出单相的ZrNiSn基Half-Heusler热电材料,并通过不同的热处理工艺调节反位缺陷浓度。采用XRD对试样的成分进行表征,并测试相关的热电性能。结果表明,该方法制备的ZrNiSn基Half-Heusler反位缺陷热电材料具有流程短、步骤少、易控制等优点。通过调控反位缺陷的浓度,能够有效的调节其变化引起的相关热电参数,从而提高材料的热电优值ZT。以上结果表明采用磁悬浮熔炼结合放电等离子体烧结工艺能够有效的制备出单相的ZrNiSn基Half-Heusler热电材料,通过不同的热处理工艺可以有效的调控反位缺陷的浓度。
应用本发明方法,通过XRD检测,不同热处理工艺的ZrNiSn热电材料均为单相,通过激光热导仪,采用四探针法直接测量得到材料的电导率,结果表明,随着扩散退火温度的升高,试样的反位缺陷逐渐减少,电导率逐渐降低。并通过计算发现反位缺陷减少时,试样的功率因子也相应的降低。最终计算结果表明,反位缺陷的增多能够有效的提升材料的热电优值ZT。本发明,获得了一种成功的制备出具有反位缺陷的ZrNiSn单相Half-Heusler热电材料的方法,并揭示了反位缺陷对ZrNiSn成分的Half-Heusler热电材料的热电性能的影响。
附图说明
图1为不同成分放电等离子体烧结后试样的XRD。
图2为不同热处理工艺的ZrNiSn成分Half-Heusler热电材料的电导率。
图3为不同热处理工艺的ZrNiSn成分Half-Heusler热电材料的功率因子。
图4为不同热处理工艺的ZrNiSn成分Half-Heusler热电材料的热电优值。
具体实施方式
以下结合实施例对本发明进一步说明:
实施例1
本实施例公开了一种具有反位缺陷成分均匀单相的ZrNiSn基Half-Heusler热电材料,按照原子比为1:1:1的成分配料并进行熔炼,其中各元素原子百分含量为:Zr:33.3%;Ni:33.3%;Sn:33.3%。
本发明的进一步改进在于:
球磨后得到的反位缺陷ZrNiSn基Half-Heusler热电材料的晶粒尺寸为0.5-2μm。
一种具有反位缺陷的单相ZrNiSn基Half-Heusler热电材料的加工方法,包括以下步骤:
(1)选料:Zr、Ni、Sn选取直径×长度为2×5mm的小颗粒。所有试样的纯度≥99.9%。
(2)为防止氧化,在手套箱中按照ZrNiSn原子比为1:1:1的名义成分进行配料。
(3)熔炼:采用磁悬浮熔炼炉,氩气保护氛围下(104-105Pa),升温至1600~1800℃后保温3min,为了保证熔炼后组织的均匀性,反复熔炼4次。
(4)球磨:首先用研钵将铸锭粗磨成粒径0.1-1mm的粉体。然后在氩气氛围下进行湿法球磨。球磨介质为无水乙醇,球料比为15:1,转速为:500r/min,球磨时间为10h。
(5)干燥处理:在手套箱中将抽滤后的粉体进行24h的自然干燥处理。
(6)烧结:采用放电等离子体烧结技术对制备的粉体进行烧结,烧结温度为1000℃,烧结压力为100MP,保温时间为15min。
(7)封管:将热处理温度为900℃试样装入直径20mm的石英玻璃管中进行真空封管,玻璃管真空度≤5×10-3Pa。
(8)热处理:将密封后的试样分别在箱式高温烧结炉中进行长时间扩散退火处理。退火温度为900℃。保温时间为24h。
(9)淬火:将保温后的试样进行快速淬火处理,以水作为淬火介质,淬火得到ZrNiSn基Half-Heusler热电材料,所述ZrNiSn基Half-Heusler热电材料晶粒尺寸为0.5-2μm。
实施例2
(1)选料:Zr、Ni、Sn选取直径×长度为2×5mm的小颗粒。所有试样的纯度≥99.9%。
(2)为防止氧化,在手套箱中按照ZrNiSn原子比为1:1:1的名义成分进行配料。
(3)熔炼:采用磁悬浮熔炼炉,氩气保护氛围下(104-105Pa),升温至1600~1800℃后保温4min,为了保证熔炼后组织的均匀性,反复熔炼3次。
(4)球磨:首先用研钵将铸锭粗磨成粒径0.1-1mm的粉体。然后在氩气氛围下进行湿法球磨。球磨介质为无水乙醇,球料比为20:1,转速为:600r/min,球磨时间为8h。
(5)干燥处理:在手套箱中将抽滤后的粉体进行20h的自然干燥处理。
(6)烧结:采用放电等离子体烧结技术对制备的粉体进行烧结,烧结温度为950℃,烧结压力为90MP,保温时间为20min。
(7)封管:将热处理温度为950℃的试样装入直径20mm的石英玻璃管中进行真空封管,玻璃管真空度≤5×10-3Pa。
(8)热处理:将密封后的试样分别在箱式高温烧结炉中进行长时间扩散退火处理。退火温度为950℃。保温时间为20h。
(9)淬火:将保温后的试样进行快速淬火处理,以水作为淬火介质,淬火得到ZrNiSn基Half-Heusler热电材料,所述ZrNiSn基Half-Heusler热电材料晶粒尺寸为0.5-2μm。
实验结果
不同成分放电等离子体烧结后试样的XRD如图1所示。从图中可以看出不同热处理工艺的ZrNiSn热电材料都为单相成分。
不同热处理工艺的ZrNiSn成分Half-Heusler热电材料的电导率如图2所示。从图2中可以看出随着退火温度的升高,试样的电导率逐渐减小,电导率在923℃时由7.35×104S/m减小到了6.25×104S/m。
不同热处理工艺的ZrNiSn成分Half-Heusler热电材料的功率因子如图3所示。从图3中可以看出随着退火温度的升高,试样的功率因子逐渐减小,功率因子在923℃时由3.31减小到了2.95。
不同热处理工艺的ZrNiSn成分Half-Heusler热电材料的热电优值如图4所示。从图4中可以看出随着退火温度的升高,试样的热电优值ZT逐渐减小,热电优值ZT在923℃时由0.63减小到了0.51。
本实施例通过采用磁悬浮熔炼结合放电等离子体烧结工艺制备出具有反位缺陷的ZrNiSn单相Half-Heusler热电材料,并通过不同的热处理工艺调节反位缺陷浓度。XRD结果显示所制备的试样都为单相。随着退火温度的升高,反位缺陷在回复的过程中拥有更高的驱动力,快速淬火后退火温度越高的试样反位缺陷的含量越少。热电性能的测试结果表明随着反位缺陷浓度的升高,试样的电导率逐渐增加,功率因子也逐渐增加,从而试样的热电优值ZT也有所提升。通过本发明,成功的制备出具有反位缺陷的ZrNiSn单相Half-Heusler热电材料,并进行了定性和定量分析,揭示了反位缺陷对ZrNiSn成分的Half-Heusler热电材料的热电性能的影响。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (8)
1.一种ZrNiSn基Half-Heusler热电材料的制备和调控反位缺陷的方法,其特征在于,包括以下步骤:
(1)按照原子比为1:1:1将Zr、Ni、Sn混合;
(2)将混合物料置于磁悬浮熔炼炉中熔炼,熔炼在氩气保护氛围下进行,将混合物料升温至1600~1800℃后保温1~5min得到铸锭;
(3)将铸锭球磨至0.5-2μm,后自然干燥获得粉体;
(4)采用放电等离子体烧结技术将粉体进行烧结,烧结温度为900-1100℃,烧结压力为80-100MPa,保温时间为5-20min;
(5)将烧结后的粉体置于真空容器中;
(6)将装有粉体的真空容器置于箱式高温烧结炉中进行长时间扩散退火处理;退火温度为800-1100℃、保温时间为12-36h;
(7)将保温后的试样进行快速淬火处理得到ZrNiSn基Half-Heusler热电材料;
步骤(3)所述球磨:首先用研钵将铸锭粗磨成粒径0.1-1mm的粉体;然后在氩气氛围下进行湿法球磨;球磨介质为无水乙醇,球料比为10:1-20:1,转速为:200-600r/min,球磨时间为5-20h。
2.根据权利要求1所述ZrNiSn基Half-Heusler热电材料的制备和调控反位缺陷的方法,其特征在于,所述Zr、Ni、Sn纯度≥99.9%。
3.根据权利要求1所述ZrNiSn基Half-Heusler热电材料的制备和调控反位缺陷的方法,其特征在于,步骤(2)所述熔炼为3-6次。
4.根据权利要求1所述ZrNiSn基Half-Heusler热电材料的制备和调控反位缺陷的方法,其特征在于,步骤(2)所述氩气保护氛围压力为104-105Pa。
5.根据权利要求1所述ZrNiSn基Half-Heusler热电材料的制备和调控反位缺陷的方法,其特征在于,步骤(3)所述干燥:在氩气氛围或者密闭无氧环境中将抽滤后的粉体进行12-48h的自然干燥处理。
6.根据权利要求1所述ZrNiSn基Half-Heusler热电材料的制备和调控反位缺陷的方法,其特征在于,步骤(5)所述真空容器的真空度≤5×10-3Pa。
7.根据权利要求1所述ZrNiSn基Half-Heusler热电材料的制备和调控反位缺陷的方法,其特征在于,步骤(7)淬火的淬火介质为水。
8.一种ZrNiSn基Half-Heusler热电材料,采用权利要求1-7任一项所述方法制备而成。
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