CN113929446B - 稀土钙钛矿高熵氧化物材料及其制备方法与应用 - Google Patents

稀土钙钛矿高熵氧化物材料及其制备方法与应用 Download PDF

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CN113929446B
CN113929446B CN202111114584.1A CN202111114584A CN113929446B CN 113929446 B CN113929446 B CN 113929446B CN 202111114584 A CN202111114584 A CN 202111114584A CN 113929446 B CN113929446 B CN 113929446B
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李领伟
成瑶
张振乾
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Hangzhou Dianzi University
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Abstract

本发明公开了一种稀土钙钛矿高熵氧化物材料及其制备方法与应用，其中RE为稀土Gd，Tb，Dy，Ho，Er中的二种或三种且各组成元素摩尔含量范围为25％‑55％、总含量为100％，TM为Mn，Fe，Co，Cu，Ni，Zn，Al，Cr中的三种或四种且各组成元素摩尔含量范围为20％‑35％、总含量为100％；RETMO3材料为单相正交钙钛矿结构，属于Pnma空间群。RETMO3高熵氧化物材料在0～5T的外场变化下，其等温磁熵变为13.6‑18.2J/kg K。本发明制备的RETMO3高熵氧化物材料应用于低温区磁制冷领域，所需设备简单，工艺简洁可靠，所得产物纯度高稳定性好，适合工业化生产。

Description

稀土钙钛矿高熵氧化物材料及其制备方法与应用
技术领域
本发明属于磁性材料技术领域，具体涉及一种应用于低温磁制冷的稀土钙钛矿高熵氧化物材料，其化学通式为RETMO3(RE为稀土Gd，Tb，Dy，Ho，Er中的二种或三种且各组成元素摩尔含量范围为25％-55％；TM为Mn，Fe，Co，Cu，Ni，Zn，Al，Cr中的三种或四种且各组成元素摩尔含量范围为20％-35％。总含量均为100％)及其制备方法与应用。
背景技术
高熵陶瓷将高熵理论引入到无机非金属领域的一种新概念材料。2015年，熵稳定氧化物(Mg0.2Zn0.2Co0.2Cu0.2Zn0.2)O被报道后，高熵陶瓷领域的研究正式开启。高熵陶瓷材料通常是指由5种或以上元素按一定比例形成的多组元固溶体。由于各组元间较高的混合熵，高熵陶瓷倾向于形成固溶体，从而具有较高的热稳定性、高强度、高硬度、巨介电常数、耐高温氧化及低热导等特性，因此高熵陶瓷成为一种极具发展潜力的新兴材料，成为新材料领域的研究热点。目前取得较大研究进度的高熵陶瓷类型大多集中在碳化物、氮化物和硼化物，钙钛矿结构高熵氧化物陶瓷及其应用尚属于研究起步阶段。此外，目前高熵陶瓷的合成方法主要是固相法或者雾化喷雾热解法，两者分别存在样品质量较低、烧结温度高、耗时长和设备复杂昂贵、制备过程复杂等问题。
磁制冷技术利用材料的磁热效应(即magnetocaloric effect，又称磁卡效应或磁熵效应)来实现制冷，通过磁制冷工质材料在变化的外加磁场中产生的磁矩有序、无序化来引起磁体的吸热和放热，从而进行制冷循环。因为不需要使用氟利昂等制冷剂，除此之外，磁致冷技术的可靠性好、易维护、噪音低、寿命长，磁制冷技术是未来最具潜力的新型制冷方式之一。目前高性能磁制冷用工质材料依然是制约磁制冷技术广泛应用的关键因素之一。
发明内容
本发明针对现有技术的不足，结合高熵材料的优点与磁制冷的需求，提供一种稀土钙钛矿高熵氧化物RETMO3材料及其制备方法与应用，特别是在磁制冷领域的应用。
一种稀土钙钛矿高熵氧化物材料，其特征在于：化学通式为RETMO3，其中RE为稀土Gd，Tb，Dy，Ho，Er中的二种或三种且各组成元素摩尔含量范围为25％-55％、总含量为100％，TM为Mn，Fe，Co，Cu，Ni，Zn，Al，Cr中的三种或四种且各组成元素摩尔含量范围为20％-35％、总含量为100％；RETMO3材料为单相正交钙钛矿结构，属于Pnma空间群；在0～5T的磁场变化下，等温磁熵变为13.6-18.2J/kg K。
一种稀土钙钛矿高熵氧化物RETMO3材料的制备方法，包括以下步骤：
步骤1：将稀土硝酸盐、过渡金属硝酸盐和柠檬酸按摩尔比1:1:2.5～1:1:3.5的摩尔比例称重并溶解在去离子水中，加热至80℃～95℃，并快速搅拌后形成凝胶；
步骤2：将步骤1制得的搅拌后的凝胶在鼓风干燥箱中于110℃～130℃下干燥3～4小时，得到粉末预产物；
步骤3：将步骤2得到的粉末预产物研磨后在500℃～750℃下煅烧4～5小时，冷却后压片得到片状化合物；
步骤4：将步骤3得到的片状化合物破碎后再次研磨，压片，在流动的空气气氛下，加热至1000℃～1200℃下烧结20～30小时后，随炉冷却至室温即可得到成品。
本方法流程简单，所制备材料纯度高，产量和产率高，制备过程对时间安排要求宽松，可有效提高产量和降低生产成本，适合工业化生产。
具体实施方式
下面对本发明做进一步的分析，但具体实施案例并不对本发明作任何限定。
实施例1：制备Gd0.5Dy0.25Ho0.25Mn0.35Fe0.35Al0.3O3磁制冷材料
步骤1：将Gd(NO3)3·6H2O、Dy(NO3)3·6H2O、Ho(NO3)3·6H2O、Mn(NO3)3、Fe(NO3)3、Al(NO3)3和柠檬酸(C6H8O7)按摩尔比10:5:5:7:7:6:50的比例称重并溶解在去离子水中，加热至90℃，并快速搅拌后形成凝胶；
步骤2：将步骤1制得的搅拌后的凝胶在鼓风干燥箱中于120℃下干燥3小时，得到粉末预产物；
步骤3：将步骤2得到的粉末预产物研磨后在600℃下煅烧4小时，冷却后压片得到片状化合物；
步骤4：将步骤3得到的片状化合物在流动的空气气氛下，加热至1100℃下烧结24小时后，随炉冷却至室温即可得到成品。测得所获成品在0～5T的磁场变化下，等温磁熵变为18.2J/kg K；
实施例2：制备Gd0.4Ho0.3Er0.3Mn0.35Fe0.35Cu0.3O3磁制冷材料
步骤1：将Gd(NO3)3·6H2O、Ho(NO3)3·6H2O、Er(NO3)3·6H2O、Mn(NO3)3、Fe(NO3)3、Cu(NO3)2和柠檬酸(C6H8O7)按摩尔比8:6:6:7:7:6:50的比例称重并溶解在去离子水中，加热至90℃，并快速搅拌后形成凝胶；
步骤2：将步骤1制得的搅拌后的凝胶在鼓风干燥箱中于120℃下干燥3小时，得到粉末预产物；
步骤3：将步骤2得到的粉末预产物研磨后在600℃下煅烧4小时，冷却后压片得到片状化合物；
步骤4：将步骤3得到的片状化合物在流动的空气气氛下，加热至1100℃下烧结24小时后，随炉冷却至室温即可得到成品。测得所获成品在0～5T的磁场变化下，等温磁熵变为17.3J/kg K；
实施例3：制备Gd0.35Tb0.3Dy0.35Mn0.35Co0.35Zn0.3O3磁制冷材料
步骤1：将Gd(NO3)3·6H2O、Tb(NO3)3·6H2O、Dy(NO3)3·6H2O、Mn(NO3)3、Co(NO3)3、Zn(NO3)2和柠檬酸(C6H8O7)按摩尔比7:6:7:7:7:6:50的比例称重并溶解在去离子水中，加热至90℃，并快速搅拌后形成凝胶；
步骤2：将步骤1制得的搅拌后的凝胶在鼓风干燥箱中于120℃下干燥3小时，得到粉末预产物；
步骤3：将步骤2得到的粉末预产物研磨后在600℃下煅烧4小时，冷却后压片得到片状化合物；
步骤4：将步骤3得到的片状化合物在流动的空气气氛下，加热至1100℃下烧结24小时后，随炉冷却至室温即可得到成品。测得所获成品在0～5T的磁场变化下，等温磁熵变为16.8J/kg K；
实施例4：制备Gd0.35Dy0.35Ho0.3Mn0.3Fe0.3Co0.2Cr0.2O3磁制冷材料
步骤1：将Gd(NO3)3·6H2O、Dy(NO3)3·6H2O、Ho(NO3)3·6H2O、Mn(NO3)3、Fe(NO3)3、Co(NO3)3、Cr(NO3)3和柠檬酸(C6H8O7)按摩尔比7:7:6:6:6:4:4:60的比例称重并溶解在去离子水中，加热至90℃，并快速搅拌后形成凝胶；
步骤2：将步骤1制得的搅拌后的凝胶在鼓风干燥箱中于120℃下干燥3小时，得到粉末预产物；
步骤3：将步骤2得到的粉末预产物研磨后在600℃下煅烧4小时，冷却后压片得到片状化合物；
步骤4：将步骤3得到的片状化合物在流动的空气气氛下，加热至1100℃下烧结24小时后，随炉冷却至室温即可得到成品。测得所获成品在0～5T的磁场变化下，等温磁熵变为16.37J/kg K；
实施例5：制备Tb0.4Dy0.3Er0.3Mn0.4Fe0.2Zn0.2Al0.2O3磁制冷材料
步骤1：将Tb(NO3)3·6H2O、Dy(NO3)3·6H2O、Er(NO3)3·6H2O、Mn(NO3)3、Fe(NO3)3、Zn(NO3)2、Al(NO3)3和柠檬酸(C6H8O7)按摩尔比4:3:3:4:2:2:2:30的比例称重并溶解在去离子水中，加热至90℃，并快速搅拌后形成凝胶；
步骤2：将步骤1制得的搅拌后的凝胶在鼓风干燥箱中于120℃下干燥3小时，得到粉末预产物；
步骤3：将步骤2得到的粉末预产物研磨后在600℃下煅烧4小时，冷却后压片得到片状化合物；
步骤4：将步骤3得到的片状化合物在流动的空气气氛下，加热至1100℃下烧结24小时后，随炉冷却至室温即可得到成品。测得所获成品在0～5T的磁场变化下，等温磁熵变为13.6J/kg K；
实施例6：制备Gd0.5Tb0.25Ho0.25Mn0.4Cu0.2Ni0.2Cr0.2O3磁制冷材料
步骤1：将Gd(NO3)3·6H2O、Tb(NO3)3·6H2O、Ho(NO3)3·6H2O、Mn(NO3)3、Cu(NO3)2、Ni(NO3)3、Cr(NO3)3和柠檬酸(C6H8O7)按摩尔比10:5:5:8:4:4:4:70的比例称重并溶解在去离子水中，加热至90℃，并快速搅拌后形成凝胶；
步骤2：将步骤1制得的搅拌后的凝胶在鼓风干燥箱中于120℃下干燥3小时，得到粉末预产物；
步骤3：将步骤2得到的粉末预产物研磨后在600℃下煅烧4小时，冷却后压片得到片状化合物；
步骤4：将步骤3得到的片状化合物在流动的空气气氛下，加热至1100℃下烧结24小时后，随炉冷却至室温即可得到成品。测得所获成品在0～5T的磁场变化下，等温磁熵变为15.9J/kg K；
实施例7：制备Gd0.5Ho0.25Er0.25Fe0.25Co0.25Ni0.25Cr0.25O3磁制冷材料
步骤1：将Gd(NO3)3·6H2O、Ho(NO3)3·6H2O、Er(NO3)3·6H2O、Fe(NO3)3、Co(NO3)3、Ni(NO3)3、Cr(NO3)3和柠檬酸(C6H8O7)按摩尔比2:1:1:1:1:1:1:12的比例称重并溶解在去离子水中，加热至90℃，并快速搅拌后形成凝胶；
步骤2：将步骤1制得的搅拌后的凝胶在鼓风干燥箱中于120℃下干燥3小时，得到粉末预产物；
步骤3：将步骤2得到的粉末预产物研磨后在600℃下煅烧4小时，冷却后压片得到片状化合物；
步骤4：将步骤3得到的片状化合物在流动的空气气氛下，加热至1100℃下烧结24小时后，随炉冷却至室温即可得到成品。测得所获成品在0～5T的磁场变化下，等温磁熵变为16.7J/kg K；
实施例8：制备Tb0.5Ho0.5Mn0.3Fe0.3Al0.2Cr0.2O3磁制冷材料
步骤1：将Tb(NO3)3·6H2O、Ho(NO3)3·6H2O、Mn(NO3)3、Fe(NO3)3、Al(NO3)3、Cr(NO3)3和柠檬酸(C6H8O7)按摩尔比5:5:3:3:2:2:35的比例称重并溶解在去离子水中，加热至90℃，并快速搅拌后形成凝胶；
步骤2：将步骤1制得的搅拌后的凝胶在鼓风干燥箱中于120℃下干燥3小时，得到粉末预产物；
步骤3：将步骤2得到的粉末预产物研磨后在600℃下煅烧4小时，冷却后压片得到片状化合物；
步骤4：将步骤3得到的片状化合物在流动的空气气氛下，加热至1100℃下烧结24小时后，随炉冷却至室温即可得到成品。测得所获成品在0～5T的磁场变化下，等温磁熵变为14.6J/kg K。

Claims (3)

1.稀土钙钛矿高熵氧化物材料，其特征在于：所述材料为Gd0.5Dy0.25Ho0.25Mn0.35Fe0.35Al0.3O3、Gd0.4Ho0.3Er0.3Mn0.35Fe0.35Cu0.3O3、Gd0.35Tb0.3Dy0.35Mn0.35Co0.35Zn0.3O3、Gd0.35Dy0.35Ho0. 3Mn0.3Fe0.3Co0.2Cr0.2O3、Tb0.4Dy0.3Er0.3Mn0.4Fe0.2Zn0.2Al0.2O3、Gd0.5Tb0.25Ho0.25Mn0.4Cu0.2Ni0.2Cr0.2O3、Gd0.5Ho0.25Er0.25Fe0.25Co0.25Ni0.25Cr0.25O3或Tb0.5Ho0.5Mn0.3Fe0.3Al0.2Cr0.2O3，所述材料为单相正交钙钛矿结构，属于Pnma空间群。
2.根据权利要求1所述的稀土钙钛矿高熵氧化物材料的制备方法，其特征在于，该方法包括以下步骤：
步骤1：将稀土硝酸盐、过渡金属硝酸盐和柠檬酸按摩尔比1:1:2.5～1:1:3.5的摩尔比例称重并溶解在去离子水中，加热至80℃～95℃，并快速搅拌后形成凝胶；
步骤2：将步骤1制得的搅拌后的凝胶在鼓风干燥箱中于110℃～130℃下干燥3～4小时，得到粉末预产物；
步骤3：将步骤2得到的粉末预产物研磨，压片，在550℃～750℃下煅烧9～15小时，得到片状化合物；
步骤4：将步骤3得到的片状化合物破碎后再次研磨，压片，在流动的空气气氛下，加热至900℃～1100℃下烧结28～50小时后，随炉冷却至室温即可得到成品。
3.如权利要求1所述稀土钙钛矿高熵氧化物材料，其特征在于：应用在磁制冷中。
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