CN110171965B - 一种npo电容器介质材料及其制备方法 - Google Patents
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- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 30
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Abstract
本发明公开了一种NPO电容器介质材料及其制备方法，所述电容器介质材料组成包含基质成分和掺杂成分，基质成分为(Bi3xZn2‑3x)(ZnxNb2‑x)O7，x=1/2~2/3；掺杂的SrTiO3占基质成分质量分数的1%~10%。本发明所述的电容器介质材料烧结温度不超过1000℃，宽温稳定性能好，介电损耗低，且成本相当低廉。
Description
技术领域
本发明涉及一种介电常数高、温度稳定性能优异且介电损耗较低的NPO电容器介质材料的制备方法，属于陶瓷电容器领域。
背景技术
电容器是一类重要的无源电子元器件，是电子、通信及信息产业中不可或缺的元器件，可以起到储存电荷、隔断直流、交流滤波、提供调谐及震荡等作用。Ⅰ类陶瓷电容器具有稳定性高、介电常数低且工作范围较窄等特性。随着电子信息技术的飞速发展，电子器件的前进方向是规格越来越小、稳定性和集成化程度更高、多功能化，因此人们对新型电子材料与器件的性能提出了更高的要求。作为电子设备中应用最广泛的电容器，人们对Ⅰ类陶瓷电容的性能提出了更高的要求。介电常数较高、损耗小、温度稳定性高的电介质陶瓷成为目前研究的重点方向之一。
Ⅰ类电容器由于受到高的温度稳定性和温度范围等因素的限制，使得介电常数不可能很高。与Ⅱ类电容器相比，Ⅰ类电容器陶瓷介质的介电常数要小得多。Ⅰ类电容器的介质陶瓷的介电常数通常都小于900。例如，微波陶瓷的介电常数普遍保持在几～几十之间，而NPO陶瓷的介质则在普遍保持几十的介电常数。而随着电子设备的不断小型化，使得电容器不断小型化。为了保持足够大的介电常数，提高介质的介电常数成为一种趋势。
现有研究中，同时保持高的介电常数、低的介电损耗以及超高温度稳定性是NPO电容器介质陶瓷的难点。Ag2O-Ta2O5-Nb2O5系统介电常数极高，在400以上，温度稳定性连续可调，但Ag属于挥发分，在烧结过程中挥发会产生空位，使得该体系的介质损耗极大，在0.01以上；MgO-TiO2-ZnO系统存在一个零温度系数区，因而该体系可以得到符合NPO使用标准的材料，有学者在该体系中掺入CaTiO3，制备出的CaTiO3-(Mg2/3Zn1/3)TiO3陶瓷材料烧结温度为1260℃，介电常数为25.1，介电损耗为0.003，容温变化率满足NPO陶瓷的使用要求，但是该体系的介电常数非常低，为20左右，且很难得到提高；BaTiO3体系介电常数高(εr＝2000)、介电损耗低，但是温度稳定性极差，有学者在该体系中掺入Ba(Zn1/3Nb2/3)O3和MnCO3，制得的陶瓷电容温度系数TCC≤±150ppm/℃，介电常数ε＝494，介电损耗tanδ＝0.0019，仍未满足NPO陶瓷对于温度稳定性方面的要求。
发明内容
基于以上现有技术的不足，本发明所解决的技术问题在于提供一种NPO电容器介质材料及其制备方法，介电常数高、宽温稳定性好、介电损耗低，且烧结温度低。
本发明为解决上述提出的问题所采用的技术方案为：
一种NPO电容器介质材料，其特征在于：该电容器介质材料组成包含基质成分和掺杂成分，基质成分为(Bi3xZn2-3x)(ZnxNb2-x)O7，x＝1/2～2/3；掺杂成分为SrTiO3，掺杂组分SrTiO3占基质成分的质量分数z％为1％～10％。优选地，x＝0.6，掺杂组分SrTiO3占基质成分质量分数的1～5％。
本发明所述NPO电容器介质材料的宽温性能较优，在应用温度范围内(-55℃～125℃)的容温变化率均小于±30ppm/℃，介电常数在90-120之间，介电损耗tanα均小于0.001，满足NPO级陶瓷电容器的使用要求。
按上述方案，所述掺杂成分SrTiO3的制备方法如下：将纳米SrTiO3(市售，粒径为100nm,纯度在99.5％以上)放于卧式球磨机上球磨20～30h，烘干后过40目筛，然后置于马弗炉中以2min/℃的升温速率升温至900～1100℃保温2～4h，以除去纳米SrTiO3中的SrCO3等杂质。自然冷却至常温后，得到掺杂成分SrTiO3粉体。
本发明还提供一种NPO电容器介质材料的制备方法，主要步骤如下：
(1)将基质成分(Bi3xZn2-3x)(ZnxNb2-x)O7与掺杂成分SrTiO3按前述比例混合后，湿法球磨20～30h，烘干后过40目筛，得到混合物料；
(2)将步骤(1)所得混合物料置于马弗炉中以2min/℃的升温速率升温至800～900℃保温2～4h，并自然冷却降至室温，得到熔块；
(3)将步骤(2)所得熔块用研钵磨碎成粉体，置于球磨罐中采用湿法球磨20～30h，然后加入粘结剂造粒并干压成型，于600℃保温2h排胶后，再于900～1000℃的温度下保温2～4h，得到NPO电容器介质材料。
进一步地，本发明提供一种更为具体的NPO电容器介质材料的制备方法，包括如下步骤：
步骤一、将纳米SrTiO3放于卧式球磨机上球磨20～30h，烘干后过40目筛，然后置于马弗炉中以2min/℃的升温速率升温至900～1100℃保温2～4h，自然冷却至常温后，得到掺杂成分SrTiO3粉体，备用；
步骤二、将基质原料ZnO、Bi2O3和Nb2O5按照4-4x:3x:2-x的摩尔比进行配料，球磨、烘干，然后升温至800～900℃预烧2～4h，得到基质成分(Bi3xZn2-3x)(ZnxNb2-x)O7粉体，x＝1/2～2/3，过筛备用；
步骤三、(1)将基质成分(Bi3xZn2-3x)(ZnxNb2-x)O7与掺杂成分SrTiO3按比例混合后，湿法球磨20～30h，烘干后过40目筛，得到(z wt％SrTiO3)-(Bi3xZn2-3x)(ZnxNb2-x)O7混合物料；(2)将步骤(1)所得混合物料置于马弗炉中以2min/℃的升温速率升温至800～900℃保温2～4h，并自然冷却降至室温，得到熔块；(3)将步骤(2)所得熔块用研钵磨碎成粉体，置于球磨罐中采用湿法球磨20～30h，然后加入粘结剂造粒并干压成型，以2min/℃的升温速率升温至600℃，并保温2h进行排胶，再于900～1000℃的温度下保温2～4h，得到NPO电容器介质材料。
与现有技术相比，本发明的有益效果是：
在现有研究中，同时保持高的介电常数以及超高温度稳定性是NPO电容器介质陶瓷的难点。本发明提供的高介电常数NPO电容器介质陶瓷，基质成分为Bi2O3-ZnO-Nb2O5，根据(Bi3xZn2-3x)(ZnxNb2-x)O7陶瓷的介电可调性，通过调节化学组成中系数x的变化，可以得到性能介于立方相和单斜相之间、介电常数较高、温度稳定性更加优异的组分，并通过掺杂SrTiO3对Bi2O3-ZnO-Nb2O5的正温度系数进行补偿，进一步提高了介电常数和温度稳定性，满足了NPO电容器使用要求。从而，本发明得到的NPO电容器介质材料相比普通的NPO陶瓷，具有更高的介电常数(在90-110之间)和更低的介电损耗(tanα均小于0.001)。本发明所提供的化学组成体系在具有优异性能的同时，采用的原料成本较低，相比于其他含稀土类的体系，其成本已经相当低廉。此外，本发明采用固相法制备陶瓷，工艺简单，且材料具有环保性(不含有毒的铅元素)，同时烧结温度较低，有利于节约能源。
附图说明
图1是x＝0.5～2/3的(Bi3xZn2-3x)(ZnxNb2-x)O7陶瓷在25℃下的介电性能图；
图2表示x＝0.5，0.55,0.6,0.6,2/3的(Bi3xZn2-3x)(ZnxNb2-x)O7在1kHz下的容温变化率图；
图3是对比例、实施例1-5制备的(z wt％SrTiO3)-(Bi3xZn2-3x)(ZnxNb2-x)O7电容器介质材料在最佳烧结温度下的XRD图，其中，x＝0.6，z＝0～5，z为0时代表对比例；
图4是对比例、实施例1-5制备的(z wt％SrTiO3)-(Bi3xZn2-3x)(ZnxNb2-x)O7电容器介质材料在在25℃下介电性能图，其中，x＝0.6，z＝0～5，z为0时代表对比例。
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明不仅仅局限于下面的实施例。
下述实施例或对比例中，原料Bi2O3、ZnO、Nb2O5、SrTiO3的纯度均大于99％；
下述实施例或对比例中，排胶后再于950～1000℃的温度下保温2～4h得到的陶瓷原片，需要进行打磨、抛光，并在陶瓷片的上下表面均匀涂覆银浆，经580℃烧银制备电极，以进行介电常数、电容温度系数等介电性能的测试。
下述实施例中，所述的粘合剂为质量分数为5wt％的聚乙烯醇溶液。
对比例
一种电容器介质陶瓷材料，其化学组成可表达为(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7，即x为0.6，z为0。其制备工艺，具体如下：
步骤一、将基质原料ZnO、Bi2O3和Nb2O5按照4-4x:3x:2-x的摩尔比进行配料，球磨、烘干，然后以2min/℃的升温速率升温至800℃预烧2h，得到基质成分(Bi3xZn2-3x)(ZnxNb2-x)O7粉体，x＝0.6；
步骤二、将步骤一所得粉体置于球磨罐中采用湿法球磨24h，然后加入粘结剂造粒并干压成型，以2min/℃的升温速率升温至600℃，并保温2h进行排胶再于900℃～1000℃之间进行烧结并保温2h，得到电容器介质陶瓷材料对比样品。
所得电容器介质材料样品结合体积密度进行分析，最佳烧结温度为950℃。测试其性能为：介电常数εr＝93，介电损耗tanδ＝0.0008，-55℃～125℃温度范围内对应的TCC≤±100ppm/℃。
实施例1
一种NPO电容器介质材料，其化学组成可表达为(1wt％SrTiO3)-(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7，即x为0.6，z为1。其制备工艺，具体如下：
步骤一、将纳米SrTiO3放于卧式球磨机上球磨24h，烘干后过40目筛，然后置于马弗炉中以2min/℃的升温速率升温至1000℃保温2h，自然冷却至常温后，得到掺杂成分SrTiO3粉体，备用；
步骤二、将基质原料ZnO、Bi2O3和Nb2O5按照4-4x:3x:2-x的摩尔比进行配料，球磨、烘干，然后以2min/℃的升温速率升温至800℃预烧2h，得到基质成分(Bi3xZn2-3x)(ZnxNb2-x)O7粉体，x＝0.6，备用；
步骤三、(1)将基质成分(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7与掺杂成分SrTiO3按质量比1:1％混合后，湿法球磨24h，烘干后过40目筛，得到混合物料；(2)将步骤(1)所得混合物料置于马弗炉中以2min/℃的升温速率升温至800℃保温2h，并自然冷却降至室温，得到熔块；(3)将步骤(2)所得熔块用研钵磨碎成粉体，置于球磨罐中采用湿法球磨24h，然后加入粘结剂(可采用：烘干后的1g粉体中加入2滴粘合剂)造粒并干压成型，于600℃保温2h排胶后，再于900～1000℃的温度下保温2h，得到NPO电容器介质材料。
实施例1所得NPO电容器介质材料结合体积密度进行分析，最佳烧结温度为950℃；测试其性能为：介电常数εr＝97，介电损耗tanδ＝0.0006，-55℃～125℃温度范围内对应的TCC≤±30ppm/℃。
实施例2
一种NPO电容器介质材料，其化学组成可表达为(2wt％SrTiO3)-(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7，即x为0.6，z为2。其制备工艺与实施例1的主要区别在于z的取值不同。
实施例2所得NPO电容器介质材料结合体积密度进行分析，最佳烧结温度为950℃；测试其性能为：介电常数εr＝103，介电损耗tanδ＝0.0001，-55℃～125℃温度范围内对应的TCC≤±30ppm/℃。
实施例3
一种NPO电容器介质材料，其化学组成可表达为(3wt％SrTiO3)-(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7，即x为0.6，z为3。其制备工艺与实施例1的主要区别在于z的取值不同。
实施例3所得NPO电容器介质材料结合体积密度进行分析，最佳烧结温度为950℃；测试其性能为：介电常数εr＝106，介电损耗tanδ＝0.0009，-55℃～125℃温度范围内对应的TCC≤±30ppm/℃。
实施例4
一种NPO电容器介质材料，其化学组成可表达为(4wt％SrTiO3)-(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7，即x为0.6，z为4。其制备工艺与实施例1的主要区别在于z的取值不同。
实施例4所得NPO电容器介质材料结合体积密度进行分析，最佳烧结温度为950℃；测试其性能为：介电常数εr＝110，介电损耗tanδ＝0.001，-55℃～125℃温度范围内对应的TCC≤±30ppm/℃。
实施例5
一种NPO电容器介质材料，其化学组成可表达为(5wt％SrTiO3)-(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7，即x为0.6，z为5。其制备工艺与实施例1的主要区别在于z的取值不同。
实施例5所得NPO电容器介质材料结合体积密度进行分析，最佳烧结温度为950℃；测试其性能为：介电常数εr＝114，介电损耗tanδ＝0.0008，-55℃～125℃温度范围内对应的TCC≤±30ppm/℃。
实施例6
一种NPO电容器介质材料，其化学组成可表达为(3wt％SrTiO3)-Bi1.5ZnNb1.5O7，即x为0.5，z为3。其制备工艺与实施例1的主要区别在于x、z的取值不同。
实施例6所得NPO电容器介质材料结合体积密度进行分析，最佳烧结温度为1000℃；测试其性能为：介电常数εr＝119，介电损耗tanδ＝0.0003，-55℃～125℃温度范围内对应的TCC≤±30ppm/℃。
实施例7
一种NPO电容器介质材料，其化学组成可表达为(2wt％SrTiO3)-Bi2Zn2/3Nb4/3O7，即x为2/3，z为2。其制备工艺与实施例1的主要区别在于x、z的取值不同。
实施例7所得NPO电容器介质材料，结合体积密度进行分析，最佳烧结温度为950℃；测试其性能为：介电常数εr＝100，介电损耗tanδ＝0.0005，-55℃～125℃温度范围内对应的TCC≤±30ppm/℃。
表1是实施例1-5及对比例分别添加质量百分比z％(分别为0wt％、1wt％、2wt％、3wt％、4wt％、5wt％)的SrTiO3的(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7电容器介质材料在1kHz下的容温变化率。
表1(z wt％SrTiO3)-(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7在1kHz下的容温变化率
图1是对比例、实施例1-5制备的(z wt％SrTiO3)-(Bi3xZn2-3x)(ZnxNb2-x)O7电容器介质材料在最佳烧结温度下的XRD图，其中，x＝0.6，z＝0～5。由图1可知，对比例中，即x＝0.6，z＝0时，所得电容器介质材料的主晶相为焦绿石单斜相；而实施例1-5中，随着SrTiO3掺量的增大，没有出现SrTiO3的杂相峰，说明SrTiO3与(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7形成了固溶体；此固溶体决定了陶瓷的介电性能，其性能以(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7为基础，受SrTiO3掺量的影响。负容温系数的SrTiO3掺量增大，(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7的容温系数下降，体系的介电常数增大。z取4、5时，出现第二相Zn2Ti3O8，这表明SrTiO3已不能完全固溶于(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7之中。
由图4、表1可知，随着z的增大，所得电容器介质材料的介电常数逐渐上升，介电损耗也逐渐上升，容温系数逐渐下降，说明对于正容温系数的(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7而言，SrTiO3的负容温系数补偿作用明显，且提高了(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7基体的介电常数。z＝1～5的电容器介质材料(z wt％SrTiO3)-(Bi1.8Zn0.2)(Zn0.6Nb1.4)O7的介电常数均在90-110之间，介电损耗tanα均小于0.001，在应用温度范围内(-55℃～125℃)的容温变化率均小于±30ppm/℃，介电常数满足NPO级陶瓷电容器的使用要求。由此可见，本发明以(Bi3xZn2-3x)(ZnxNb2-x)O7为基质成分，掺入少量的SrTiO3可明显改善BZN基陶瓷的宽温稳定性。
以上所述是本发明的优选实施方式而已，当然不能以此来限定本发明之权利范围，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和变动，这些改进和变动也视为本发明的保护范围。
Claims (6)
1.一种NPO电容器介质材料，其特征在于，该电容器介质材料组成包含基质成分和掺杂成分，基质成分为(Bi3xZn2-3x)(ZnxNb2-x)O7，x=1/2~2/3；掺杂成分为SrTiO3，掺杂组分SrTiO3占基质成分的质量分数z%为1%~10%。
2.根据权利要求1所述的一种NPO电容器介质材料，其特征在于，x=0.6，掺杂组分SrTiO3占基质成分质量分数的1~5%。
3.根据权利要求1所述的一种NPO电容器介质材料，其特征在于，在应用温度-55℃～125℃范围内的容温变化率均小于±30ppm/℃，介电常数在90-120之间，介电损耗tanα均小于0.001。
4.根据权利要求1所述的一种NPO电容器介质材料，其特征在于，所述掺杂成分SrTiO3的制备方法如下：将纳米SrTiO3球磨20~30h，烘干后过筛，然后升温至900~1100℃保温2~4h，自然冷却至常温后，得到掺杂成分SrTiO3粉体。
5.权利要求1所述的NPO电容器介质材料的制备方法，其特征在于，主要步骤如下：
（1）将基质成分(Bi3xZn2-3x)(ZnxNb2-x)O7与掺杂成分SrTiO3按权利要求1所述比例混合后，湿法球磨20~30h，烘干后过筛，得到混合物料；
（2）将步骤（1）所得混合物料升温至800~900℃保温2~4h，并自然冷却降至室温，得到熔块；
（3）将步骤（2）所得熔块用研钵磨碎成粉体，置于球磨罐中采用湿法球磨20~30h，然后加入粘结剂造粒并干压成型，排胶后，再于900~1000℃的温度下保温2~4h，得到NPO电容器介质材料。
6.权利要求1所述的NPO电容器介质材料的制备方法，其特征在于，主要步骤如下：
步骤一、将纳米SrTiO3放于卧式球磨机上球磨20~30h，烘干后过筛，然后置于马弗炉中升温至900~1100℃保温2~4h，自然冷却至常温后，得到掺杂成分SrTiO3粉体，备用；
步骤二、将基质原料ZnO、Bi2O3和Nb2O5按照4-4x:3x:2-x的摩尔比进行配料，球磨、烘干，然后升温至800~900℃预烧2~4h，得到基质成分(Bi3xZn2-3x)(ZnxNb2-x)O7粉体，x=1/2~2/3，备用；
步骤三、（1）将基质成分(Bi3xZn2-3x)(ZnxNb2-x)O7与掺杂成分SrTiO3按权利要求1所述比例混合后，湿法球磨20~30h，烘干后过筛，得到(z wt%SrTiO3)-(Bi3xZn2-3x) (ZnxNb2-x)O7混合物料；（2）将步骤（1）所得混合物料置于马弗炉中升温至800~900℃保温2~4h，并自然冷却降至室温，得到熔块；（3）将步骤（2）所得熔块用研钵磨碎成粉体，置于球磨罐中采用湿法球磨20~30h，然后加入粘结剂造粒并干压成型，排胶后，再升温至900~1000℃的温度下保温2~4h，得到NPO电容器介质材料。
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