CN114605151A - Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料及制备方法 - Google Patents
Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料及制备方法 Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 50
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 31
- 239000010937 tungsten Substances 0.000 title claims abstract description 31
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 8
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 4
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 4
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 4
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Abstract
本发明公开了Gd‑Ta共掺杂钨青铜结构铁电储能陶瓷材料，该铁电储能陶瓷材料的结构式为Sr(0.53‑0.15x)Ba0.47GdxNb2‑yTayO6，其中，x的取值为0.01～0.1，y的取值为0.1～0.5。本发明还公开了其制备方法，具体为：称取BaCO3、SrCO3、Gd2O3、Nb2O5、Ta2O5，充分混合球磨，干燥后进行预烧，将预烧粉经造粒、压片、排胶后，进行烧结，即可。通过在陶瓷材料中掺杂Gd和Ta，不但获得了高储能密度，且显著提高了其储能效率，并改善了其储能性能的温度稳定性，在140℃下击穿场强可以达到400kV·cm‑1，储能密度达到85％。
Description
技术领域
本发明属于陶瓷材料制备技术领域，具体涉及一种Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料，还涉及其制备方法。
背景技术
近年来，无铅压铁电材料除了研究提高压铁电性能以期替代含铅材料外，还在应变、电卡、热电、光电、发光等方面发现新的功能特性，使其受到越来越多的关注。而电介质陶瓷作为一种先进储能材料，由于其具有功率密度高(最高可达108W/kg)、工作电压高、充放电速度快和工作温度范围宽等优点，在混合动力汽车、微波通讯、脉冲功率武器、电磁弹射、脉冲功率电子器件等方面应用非常广泛。
钨青铜结构材料，由于其灵活多变的可调性，不同的离子掺杂或A位、B位离子的无序排布，可使其电学性能的调控性很大，故受到了广泛关注，但其储能性能的研究主要集中在Sr2NaNb5O15充满型结构体系，但Na元素在高温烧结过程中的挥发不利于获得致密陶瓷，而且该陶瓷体系不仅具有铁电-顺电相转变，还具有铁弹相转变，其复杂的相变过程导致高温下畴翻转和迁移产生能量耗散，降低击穿场强，限制其在储能方面的应用；因此，面对储能设备高集成化和小型化的发展，迫切需要寻求和开发具有高性能的电介质储能材料。
具有未充满型钨青铜结构的SrxBa1-xNb2O6(SBN)体系，其是SrNb2O6和BaNb2O6的固溶体，固溶范围在x＝0.26～0.87，具有Sr/Ba比连续可调的特点，因此可以通过调节组分来改变电光性能，介电性能和热释电性能，使其满足在不同技术领域的需求。但该陶瓷在高温烧结时容易出现晶粒异常长大现象和液相熔融区域，很大程度地降低致密度并破坏电性能和储能性能。
发明内容
本发明的目的是提供Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料，显著提高了其储能效率和温度稳定性。
本发明所采用的技术方案是，Gd-Ta共掺杂钨青铜结构铁电储能陶瓷，该铁电储能陶瓷材料的结构式为Sr(0.53-0.15x)Ba0.47GdxNb2-yTayO6，其中，x的取值为0.01～0.1，y的取值为0.1～0.5。
优选的，x的取值为0.02、y的取值为0.2。
本发明所采用的另一技术方案是，Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料的制备方法，具体按照以下步骤实施：
步骤1，按照Sr(0.53-0.15x)Ba0.47GdxNb2-yTayO6的化学计量比分别称取纯度为99.00％以上的BaCO3、SrCO3、Gd2O3、Nb2O5、Ta2O5，充分混合球磨，干燥，得到原料混合物；
步骤2，将原料混合物进行预烧，得到预烧粉；
步骤3，将预烧粉经造粒、压片、排胶后，进行烧结，得到Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料。
本发明的特点还在于，
步骤1中，球磨时间为16～24小时；干燥温度为80～100℃，干燥时间为12～24小时。
步骤2中，预烧温度为900～1250℃，预烧时间为2～6小时。
步骤3中，具体为：将预烧粉在聚乙烯醇粘结剂作用下进行造粒、200MPa冷等静压下保持1min压片，随后以1℃/min升温至600℃排胶，并在1280～1340℃的条件下烧结2～6小时，即可得到Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料。
本发明另一目的是提供Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料的制备方法。
本发明的有益效果是：通过在Sr0.53Ba0.47Nb2O6陶瓷体系中掺杂Gd和Ta，不但获得了高储能密度，且显著提高了其储能效率，同时储能性能的温度稳定性也显著提高。
附图说明
图1是对比例1、对比例2及实施例1～4制备的陶瓷材料的XRD图。
图2是对比例1及实施例1～4制备的陶瓷材料的电滞回线图。
图3是对比例1及实施例1～4制备的陶瓷材料的室温储能性能图。
图4a是实施例2制备的陶瓷材料在不同温度下的电滞回线图；
图4b是实施例2制备的陶瓷材料的储能参数随温度变化图；
图5是对比例2制备的陶瓷材料在不同测试频率下的介电常数和介电损耗图；
图6是对比例1及实施例1～4制备的陶瓷材料在1kHz下的介电图谱；
图7是对比例1及实施例1～4制备的陶瓷材料在1kHz下的室温介电常数对比图。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料，其结构式为Sr(0.53-0.15x)Ba0.47GdxNb2-yTayO6，其中，x的取值为0.01～0.1，y的取值为0.1～0.5；
优选的，x的取值为0.02、y的取值为0.2。
本发明Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料的制备方法，具体按照以下步骤实施：
步骤1，按照Sr(0.53-0.15x)Ba0.47GdxNb2-yTayO6的化学计量比分别称取纯度为99.00％以上的BaCO3、SrCO3、Gd2O3、Nb2O5、Ta2O5，充分混合球磨16～24小时，在80～100℃的条件下干燥12～24小时，得到原料混合物；
步骤2，将原料混合物在900～1250℃的条件下预烧2～6小时，得到预烧粉；
优选的，将原料混合物在1100℃的条件下预烧4小时；
步骤3，将预烧粉在聚乙烯醇(PVA)粘结剂作用下进行造粒、200MPa冷等静压下保持1min压片，随后以1℃/min升温至600℃排胶，并在1280～1340℃的条件下烧结2～6小时，得到Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料；
优选的，将预烧粉经造粒、压片、排胶后，在1330℃的条件下烧结2小时。
本发明通过Gd-Ta共掺杂Sr0.53Ba0.47Nb2O6陶瓷体系抑制了钨青铜结构陶瓷非等轴晶粒的异常长大，形成了致密的铁电储能材料，减少了电场下的能量耗散，另外，该陶瓷组成中不涉及高温烧结过程中易于挥发的Bi、Na、K等元素，易于器件的集成化，操作简单，对设备、人力和场地要求低，有望实现工业化生产。
实施例1
步骤1，按照Sr0.515Ba0.47Gd0.01Nb1.9Ta0.1O6的化学计量分别称取纯度为99.00％的SrCO3 2.5760g、纯度为99.00％的BaCO3 3.1425g、纯度为99.90％的Nb2O5 8.4786g、纯度为99.85％的Ta2O5 0.7422g、纯度为99.99％的Gd2O3 0.0608g，装入尼龙罐中，以锆球为磨球、无水乙醇为球磨介质，用球磨机400转/分钟球磨16小时，置于干燥箱内在80℃下干燥15小时，用研钵研磨30分钟，过80目筛，得到原料混合物，
步骤2，将原料混合物置于氧化铝坩埚内，用玛瑙棒压实，使其压实密度为1.5g/cm3，加盖，置于电阻炉内，以3℃/分钟的升温速率升温至1100℃预烧4小时，自然冷却至室温，出炉，用研钵研磨10分钟，过120目筛，得到预烧粉；
步骤3，向预烧粉中加入质量分数为5％的聚乙烯醇水溶液(聚乙烯醇水溶液的质量是预烧粉质量的50％)，造粒，过100目筛，制成球状粉粒，将球状粉粒放入直径为15mm的不锈钢模具内，用冷等静压在200MPa的压力下将其压制成厚度为1.5mm的圆柱状坯件，将圆柱状坯件放在氧化锆平板上，将氧化锆平板置于氧化铝密闭匣钵中，先以1℃/分钟的升温速率升温至500℃，保温2小时排胶，冷却至室温，再以5℃/分钟的升温速率升温至1000℃，在以3℃/分钟的升温速率升温至1330℃，烧结2小时，随炉自然冷却至室温，得到Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料。
实施例2
本实施例的步骤1中，按照Sr0.5Ba0.47Gd0.02Nb1.8Ta0.2O6的化学计量分别称取纯度为99.00％的SrCO3 2.4548g、纯度为99.00％的BaCO3 3.0845g、纯度为99.90％的Nb2O57.8842g、纯度为99.85％的Ta2O5 1.4571g、纯度为99.99％的Gd2O3 0.1194g，其他步骤与实施例1相同，得到Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料。
实施例3
本实施例的步骤1中，按照Sr0.485Ba0.47Gd0.03Nb1.7Ta0.3O6的化学计量分别称取纯度为99.00％的SrCO3 2.3381g、纯度为99.00％的BaCO3 3.0287g、纯度为99.90％的Nb2O57.3114g、纯度为99.85％的Ta2O5 2.1460g、纯度为99.99％的Gd2O3 0.1758g，其他步骤与实施例1相同，得到Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料。
实施例4
本实施例的步骤1中，按照Sr0.455Ba0.47Gd0.05Nb1.5Ta0.5O6的化学计量分别称取纯度为99.00％的SrCO3 2.1168g、纯度为99.00％的BaCO3 2.9229g、纯度为99.90％的Nb2O56.2258g、纯度为99.85％的Ta2O5 3.4517g、纯度为99.99％的Gd2O3 0.2828g，
其他步骤与实施例1相同，得到Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料。
对比例1
按照Sr0.53Ba0.47Nb2O6的化学计量分别称取纯度为99.00％的SrCO3 2.7017g、纯度为99.00％的BaCO3 3.2026g、纯度为99.90％的Nb2O5 9.0956g，其他步骤与实施例1相同，得到Sr0.53Ba0.47Nb2O6陶瓷材料。
对比例2
按照Sr0.485Ba0.47Gd0.03Nb2O6的化学计量分别称取纯度为99.00％的SrCO32.7017g、纯度为99.00％的BaCO3 3.2026g、纯度为99.99％的Gd2O3 0.1864g、纯度为99.90％的Nb2O5 9.1221g，其他步骤与实施例1相同，得到Gd掺杂钨青铜结构铁电储能陶瓷材料。
上述对比例1和2及实施例1～4制备的陶瓷材料分别采用D/max-2200X型射线衍射仪(由日本理学公司生产)进行XRD测试、采用铁电工作站及连接控温装置(THMS600)对其铁电性能进行测试，并评估储能特性及其温度稳定性，结果见图1～4。由图1可见，对比例1、对比例2及实施例1～4制备陶瓷材料均为纯的四方钨青铜相。由图2可见，对比例2中通过在Sr0.53Ba0.47Nb2O6陶瓷材料中掺杂Gd虽然使陶瓷材料的极化强度增加，但其电场强度较弱，本发明通过在Sr0.53Ba0.47Nb2O6陶瓷材料中同时掺杂Gd和Ta，不但使陶瓷材料极化和电场强度同时增强，而且相对于对比例2，陶瓷材料的电滞回线变细，其储能密度和效率如图3所示，在实施例2中储能性能最为优异，其击穿场强为470kV·cm-1、最大极化强度为42.95μC·cm-2、室温储能性能为6.23J·cm-3、效率为83.8％，如图4所示，且在室温到140℃间其储能性能比较稳定，电场强度可以达到400kV/cm，储能密度仍有85％。
将对比例1、对比例2及实施例1～4制备的陶瓷材料表面依次用320目、800目、1500目砂纸抛光至0.5～0.6mm厚，然后在陶瓷上下表面涂覆厚度为0.01～0.03mm的银浆，置于电阻炉中840℃保温30分钟。采用HIOKI3532-50和Agilient4980A型精密阻抗分析仪(由安捷伦科技有限公司生产)等进行陶瓷介电性能测试，结果见图5～7。由图5～7可见，与对比例1和对比例2的陶瓷材料相比，本发明通过在陶瓷材料中同时掺杂Gd和Ta，陶瓷的弛豫性明显增强，在x取值为0.02、y的取值为0.2时，材料的室温介电常数为1845、居里温度为265K。
本发明制备的Gd-Ta共掺杂Sr0.53Ba0.47Nb2O6陶瓷材料的弛豫性明显增强，B位Ta的引入诱发极化单元BO6八面体发生畸变，同时非等价离子Gd3+取代Sr2+的引入造成离子无序分布及形成局域电场和弹性场，易于打破铁电畴的长程分布，形成纳米极化微畴，显著提高材料的耐击穿强度，即实现了高储能密度和效率，同时储能性能的温度稳定性也显著提高。
Claims (6)
1.Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料，其特征在于，该铁电储能陶瓷材料的结构式为Sr(0.53-0.15x)Ba0.47GdxNb2-yTayO6，其中，x的取值为0.01～0.1，y的取值为0.1～0.5。
2.如权利要求1所述的Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料，其特征在于，x的取值为0.02、y的取值为0.2。
3.如权利要求1所述的Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料的制备方法，其特征在于，具体按照以下步骤实施：
步骤1，按照Sr(0.53-0.15x)Ba0.47GdxNb2-yTayO6的化学计量比分别称取纯度为99.00％以上的BaCO3、SrCO3、Gd2O3、Nb2O5、Ta2O5，充分混合球磨，干燥，得到原料混合物；
步骤2，将原料混合物进行预烧，得到预烧粉；
步骤3，将预烧粉经造粒、压片、排胶后，进行烧结，得到Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料。
4.如权利要求3所述的Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料的制备方法，其特征在于，所述步骤1中，球磨时间为16～24小时；干燥温度为80～100℃，干燥时间为12～24小时。
5.如权利要求3所述的Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料的制备方法，其特征在于，所述步骤2中，预烧温度为900～1250℃，预烧时间为2～6小时。
6.如权利要求3所述的Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料的制备方法，其特征在于，所述步骤3中，具体为：将预烧粉在聚乙烯醇粘结剂作用下进行造粒、200MPa冷等静压下保持1min压片，随后以1℃/min升温至600℃排胶，并在1280～1340℃的条件下烧结2～6小时，即可得到Gd-Ta共掺杂钨青铜结构铁电储能陶瓷材料。
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