CN101276659A - 电介质陶瓷及层合陶瓷电容器 - Google Patents

电介质陶瓷及层合陶瓷电容器 Download PDF

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CN101276659A
CN101276659A CNA2008100879259A CN200810087925A CN101276659A CN 101276659 A CN101276659 A CN 101276659A CN A2008100879259 A CNA2008100879259 A CN A2008100879259A CN 200810087925 A CN200810087925 A CN 200810087925A CN 101276659 A CN101276659 A CN 101276659A
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西川润
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Taiyo Yuden Co Ltd
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Abstract

本发明提供一种具有满足X8R特性的温度特性且高温环境下的比电阻高的层合陶瓷电容器及构成该层合陶瓷电容器的电介质陶瓷。其特征在于，以由(Bi0.5Na0.5)xBa1－xTiO3所表示的、x为0.05～0.2的化合物为主成分，作为第一副成分，相对于100mol所述主成分，含有以换算成1分子中1原子的氧化物计为0.25mol～1.5mol的选自Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb及Y中的至少1种稀土类金属、和以换算成1分子中1原子的氧化物计为0.2mol～1.5mol的Mg、和以换算成1分子中1原子的氧化物计为0.03mol～0.60mol的选自V、Cr及Mn中的至少1种金属。

Description

电介质陶瓷及层合陶瓷电容器
技术领域
本发明涉及电介质陶瓷和使用该电介质陶瓷的层合陶瓷电容器，本发明能够得到具有由Ni或Ni合金构成的内部电极、在150℃～200℃的温度区域内静电电容的温度变化小的层合陶瓷电容器。
背景技术
对用于便携设备、通信设备等电子设备的层合陶瓷电容器的小型化、大容量化的要求逐渐提高。作为上述小型大容量的层合陶瓷电容器，例如有如特开2001-39765号公报公开的由Ni构成内部电极的层合陶瓷电容器。该层合陶瓷电容器满足X7R特性(以25℃为基准，-55℃～+125℃的温度范围内的介电常数的变化率在±15％以内)。
但是，近年来，根据用途的不同，要求上述层合陶瓷电容器在更严格的环境中具有可靠性。例如，在汽车的发动机舱(engine room)内搭载的发动机电子控制单元、防抱死制动系统等车载电子装置中开始使用层合陶瓷电容器。由于要求上述车载电子装置在低于-20℃的低温环境下或高于+130℃的高温环境下均可稳定地运行，所以要求其中使用的层合陶瓷电容器在上述环境下也具有良好的温度稳定性。
为了满足上述要求，例如，公开了如特开2005-272263号公报所示的、满足X8R特性(以25℃为基准，-55℃～+150℃的温度范围内的介电常数或静电电容的变化率在±15％以内)的电介质陶瓷组合物及层合陶瓷电容器。
[专利文献1]特开2001-39765号公报
[专利文献2]特开2005-272263号公报
发明内容
上述专利文献1及专利文献2公开的层合陶瓷电容器由以钛酸钡为主体的电介质陶瓷组合物构成。此钛酸钡的居里点为125℃，超过125℃时介电常数急剧降低。因此，在-55℃～125℃的范围内，可以使介电常数或静电电容的变化率在±15％以内，但在也包含超过125℃的温度区域时使介电常数或静电电容的变化率在±15％以内非常困难。另外，为了进一步实现小型大容量化，使内部电极间的电介质陶瓷厚度进一步变薄时，具有可能不能得到充分的绝缘电阻的问题。特别是具有在超过125℃的高温环境下的绝缘电阻不充分的问题。
本发明是为了解决上述课题而提出的，其第一目的在于提供一种层合陶瓷电容器，所述层合陶瓷电容器具有满足X8R特性的温度特性、且在125℃～200℃高温环境下的绝缘电阻换算为内部电极间的电介质陶瓷的比电阻为100MΩm或高于100MΩm。另外，第二目的在于提供用于上述层合陶瓷电容器的电介质陶瓷。
本发明的第一方案是提供一种电介质陶瓷，所述电介质陶瓷以由(Bi0.5Na0.5)xBa1-xTiO3所表示的、x为0.05～0.2的具有钙钛矿结构的化合物为主成分，作为第一副成分，相对于100mol所述主成分，含有以换算成1分子中1原子的氧化物计为0.25mol～1.5mol的选自Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb及Y中的至少1种稀土类金属、和以换算成1分子中1原子的氧化物计为0.2mol～1.5mol的Mg、和以换算成1分子中1原子的氧化物计为0.03mol～0.60mol的选自V、Cr及Mn中的至少1种金属，作为第二副成分，含有SiO2或以SiO2为主体的玻璃成分。根据此第一方案，能够得到可用于温度特性满足X8R特性的层合陶瓷电容器的、且125℃～200℃的高温环境下的比电阻为100MΩm或高于100MΩm的电介质陶瓷。
另外，本发明的第二方案提供一种层合陶瓷电容器，具有大致长方体形状的陶瓷层合体、和在该陶瓷层合体中间隔电介质陶瓷相对向且交替引出到不同的端面而形成的内部电极、和形成于所述陶瓷层合体的两端面上并与引出到该端面上的所述内部电极分别电连接的外部电极，其特征在于，所述电介质陶瓷由上述第一方案所示的电介质陶瓷构成，所述内部电极由Ni或Ni合金形成。根据此第二方案，能够得到温度特性满足X8R特性且125℃～200℃高温环境下的绝缘电阻为100MΩm或高于100MΩm、并且高温加速寿命特性在200℃-20V/μm下为10000秒或超过10000秒的层合陶瓷电容器。
根据本发明，能够提供一种具有满足X8R特性的温度特性且高温环境下的绝缘电阻为100MΩm或高于100MΩm、并且高温加速寿命特性在200℃-20V/μm下为10000秒或超过10000秒的层合陶瓷电容器。另外，根据本发明还能提供一种用于上述层合陶瓷电容器的电介质陶瓷。
附图说明
[图1]是表示层合陶瓷电容器剖面的模式图。
符号说明
1  层合陶瓷电容器
2  陶瓷层合体
3  电介质陶瓷
4  内部电极
5  外部电极
6  第一镀层
7  第二镀层
具体实施方式
对本发明的电介质陶瓷的实施方案进行说明。本发明的电介质陶瓷，以(Bi0.5Na0.5)XBa1-XTiO3为主成分，使第一副成分和第二副成分以上述组成比与该主成分烧结而成，所述第一副成分含有Mg的氧化物、选自V、Cr及Mn中的至少1种金属的氧化物及选自Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb及Y中的至少1种稀土类金属的氧化物，所述第二副成分由SiO2、或B2O3-SiO2类玻璃或Li2O-SiO2类玻璃等玻璃成分构成。
上述电介质陶瓷，可以如下获得。首先，合成作为主成分的(Bi0.5Na0.5)XBa1-XTiO3。准备起始原料，例如相对于1mol的TiO2称量1-xmol的Ba2CO3、0.25xmol的Bi2O3、0.25xmol的Na2CO3，使x在0.05～0.2的范围内。向上述原料中加入水，使用球磨机、珠磨机(beadmill)、分散磨(Dispermill)等进行湿式混合。干燥混合物，将此干燥物在900℃下保持1小时，煅烧，由此可以得到作为主成分的(Bi0.5Na0.5)XBa1-XTiO3粉末。此(Bi0.5Na0.5)XBa1-XTiO3的居里点与BaTiO3相比移到高温侧，居里点在150℃～200℃的范围内。因此，与目前使用BaTiO3的电介质陶瓷相比，在125℃～200℃下的介电常数的降低减小，能够容易地使介电常数的变化率在±15％以内。
然后，添加下述物质，即，相对于100mol所得的主成分的粉末，添加以换算成1分子中1原子的氧化物计为0.25mol～1.5mol的稀土类金属、以换算成1分子中1原子的氧化物计为0.2mol～1.5mol的Mg、及以换算成1分子中1原子的氧化物计为0.03mol～0.60mol的V、Cr或Mn等过渡金属，进而，添加SiO2或以SiO2为主体的玻璃成分，将其湿式混合，使其干燥，形成电介质陶瓷组合物。此电介质陶瓷组合物可以用于形成层合陶瓷电容器的电介质陶瓷层。此处，所谓“换算成1分子中1原子的氧化物”是指，换算成1分子中具有1个金属原子的氧化物，例如为Ho2O3时，换算成HoO3/2。需要说明的是，SiO2或以SiO2为主体的玻璃成分是为了使电介质陶瓷在1150～1400℃下烧结而添加的成分，对添加量没有特殊的限定，但在烧结后玻璃成分于电介质陶瓷和内部电极之间析出，为了不引起介电常数降低，优选相对于100质量份主成分，添加0.5～20质量份SiO2或以SiO2为主体的玻璃成分。
下面说明本发明实施方案中的层合陶瓷电容器。如图1所示，本实施方案的层合陶瓷电容器1具有大致长方体形状的陶瓷层合体2，所述陶瓷层合体2具有电介质陶瓷3、间隔该电介质陶瓷3相对向且交替引出到不同的端面而形成的内部电极4，在该陶瓷层合体2的两端面上形成外部电极5，使其与内部电极电连接。根据需要，在上述外部电极5上形成用于保护外部电极5的第一镀层6、用于提高具焊锡润湿性(solderwettability)的第二镀层7。
接下来，对层合陶瓷电容器1的制造方法进行说明。首先，准备本发明的电介质陶瓷组合物。将其与丁缩醛类或丙烯酸类有机粘合剂、溶剂及其他添加剂混合，形成陶瓷浆料。使用辊涂机等涂布装置使该陶瓷浆料薄片化，形成作为电介质陶瓷3的具有规定厚度的陶瓷印刷电路基板(陶瓷印刷电路基板成型步骤)。
通过丝网印刷在该陶瓷印刷电路基板上以规定图案形状涂布Ni或Ni合金的导电糊料，形成作为内部电极4的导电体层(内部电极形成步骤)。层合所需片数的形成有导电体层的陶瓷印刷电路基板后，压接，形成未烧成陶瓷层合体。将其切割成单个的芯片后，在大气中或氮气等非氧化性气体中脱粘合剂(层合体形成步骤)。
脱粘合剂后，在单个芯片的内部电极露出面上涂布导电糊料，形成作为外部电极5的导电体膜(外部电极形成步骤)。将上述形成有导电体膜的单个芯片在规定温度的氮-氢气氛(氧分压为10-10atm左右)中烧成(烧成步骤)。需要说明的是，外部电极5也可以在烧成单个芯片形成陶瓷层合体2后，在内部电极露出面上涂布含有玻璃料的导电糊料后进行烧结而形成。外部电极5除可以使用与内部电极相同的金属以外，还可以使用Ag、Pd、AgPd、Cu、Cu合金等。可以进一步在外部电极5上由Ni、Cu等形成第一镀层6，在第一镀层6上由Sn或Sn合金等形成第二镀层7，得到层合陶瓷电容器1。
[实施例]
首先，准备主成分(Bi0.5Na0.5)XBa1-XTiO3的起始原料，考虑到例如在之后的湿式混合中离子溶出的部分或烧成时蒸发的部分，秤量Ba2CO3、TiO2、Bi2O3及Na2CO3，使x为表1的值。然后，用球磨机将准备的起始原料湿式混合15小时，干燥后在900℃下煅烧1小时，得到主成分的粉末。需要说明的是，No.1为通常的BaTiO3。
[表1]
Figure A20081008792500081
接下来，相对于100mol所得的主成分(Bi0.5Na0.5)XBa1-XTiO3，添加稀土类金属的氧化物、MgO及过渡金属的氧化物，使其量以换算成1分子中1原子的氧化物计，分别为表1所示的量，进而，相对于100质量份主成分(Bi0.5Na0.5)XBa1-XTiO3，添加10质量份SiO2，将上述混合物用球磨机湿式混合15小时，干燥，得到电介质陶瓷粉末。
在上述粉末中加入聚乙烯醇缩丁醛、有机溶剂、增塑剂，进行混合，形成陶瓷浆料。利用辊涂机将该陶瓷浆料涂布在PET薄膜上使其薄片化，得到厚度为5μm宽度20cm的连续薄片形状的陶瓷印刷电路基板。通过丝网印刷在该陶瓷印刷电路基板上涂布Ni内部电极糊料，形成7.6mm×1.6mm的矩形形状糊料膜以0.4mm间隔成格子状排列的内部电极图案。将形成内部电极图案的陶瓷印刷电路基板冲裁成15cm×15cm的大小，内部电极图案沿长度方向交替错开半个图案，层合21片，形成了层合体。将此层合体进行压接，然后，将其切割成4.0mm×2.0mm大小，形成毛坯芯片(raw chip)。将该毛坯芯片在氮气氛中于500℃下脱粘合剂，涂布Ni外部电极糊料，在还原气氛(氮-氢氛围、氧分压10-10atm)中，于1200℃下保持1小时，进行烧成，然后以750℃/hr的降温速度降至室温。
测定如上所述得到的大小为3.2×1.6mm、电介质陶瓷层厚为3μm的层合陶瓷电容器的电容变化率(温度特性)、绝缘电阻及高温加速寿命特性，结果示于表2。需要说明的是，电容变化率用以25℃时的静电电容为基准的变化率表示。另外，在-55℃～125℃范围内，除No.7的试样外，各试样的电容变化率均在±15％的范围内。另外，绝缘电阻如下测定：在温度为200℃、测定电压为7V/μm的条件下使兆欧计(Megohm Meter)的测定接头与外部电极接触，测定电阻值，由内部电极的交叉面积和内部电极之间的电介质陶瓷厚度计算比电阻，随机选择10个试样进行上述计算，取其平均值。另外，高温加速寿命特性如下测定：在200℃、20V/μm的负荷下，随机选择10个试样进行测定，将上述10个试样的电阻值降低至1MΩ以下的时间的平均值作为高温加速寿命特性。
[表2]
Figure A20081008792500101
由改变x值的试样序号1～7的结果可知，通过使主成分(Bi0.5Na0.5)XBa1-XTiO3的x值在0.05～0.20的范围内，能够得到温度特性满足X8R特性且高温环境下的比电阻为100MΩm或高于100MΩm的电介质陶瓷，进而能够得到高温加速寿命特性在200℃-20V/μm下为10000秒或超过10000秒的层合陶瓷电容器。另外，通过使x值在0.1～0.2的范围内，能够得到-55℃～200℃温度范围内以25℃为基准的静电电容的变化率在±15％范围内的温度特性。需要说明的是，x值在本发明的范围之外时，在125℃～200℃温度范围内以25℃为基准的静电电容的变化率不在±15％范围内。
由增减了稀土类金属(Ho)氧化物的添加量的试样序号8～13的结果可知，通过使其添加量在相对于100mol主成分为0.25mol～1.50mol范围内，能够得到温度特性满足X8R特性且高温环境下的比电阻为100MΩm或高于100MΩm的电介质陶瓷，进而能够得到高温加速寿命特性在200℃-20V/μm下为10000秒或超过10000秒的层合陶瓷电容器。需要说明的是，稀土类金属氧化物的添加量在本发明的范围之外时，烧结不充分或高温环境下的比电阻低于100MΩm、高温加速寿命特性在200℃-20V/μm下不足10000秒。
由增减了Mg氧化物添加量的试样序号14～19的结果可知，通过使其添加量相对于100mol主成分在0.20mol～1.50mol的范围内，能够得到温度特性满足X8R特性且高温环境下的比电阻为100MΩm或高于100MΩm的电介质陶瓷，进而能够得到高温加速寿命特性在200℃-20V/μm下为10000秒或超过10000秒的层合陶瓷电容器。需要说明的是，Mg氧化物的添加量在本发明的范围之外时，烧结不充分或高温环境下的比电阻低于100MΩm、高温加速寿命特性在200℃-20V/μm下不足10000秒。
由增减了过渡金属(Mn)氧化物的添加量的试样序号20～25的结果可知，通过使其添加量相对于100mol主成分在0.03mol～0.60mol的范围内，能够得到温度特性满足X8R特性且高温环境下的比电阻为100MΩm或高于100MΩm的电介质陶瓷组合物，进而，能够得到高温加速寿命特性在200℃-20V/μm下为10000秒或超过10000秒的层合陶瓷电容器。需要说明的是，Mn氧化物的添加量在本发明的范围之外时，高温环境下的比电阻低于100MΩm。
由将稀土类金属取代为Ho以外的稀土类金属的试样序号26～34的结果可知，即使将稀土类金属取代为Ho以外的稀土类金属，仍能得到相同的效果。另外，由使用Ho和Dy 2种稀土类金属的试样No.35的结果可知，即使使用2种稀土类元素，也可得到相同的效果。
根据将过渡金属取代为Mn以外的过渡金属的试样序号36～37的结果，即使将Mn取代为V或Cr，仍能得到相同的效果。另外，根据使用V和Mn 2种过渡金属的试样序号38的结果，即使使用2种过渡金属，也可以得到相同的效果。
由上述结果可知，根据本发明，可以得到具有满足X8R特性的温度特性且高温环境下的比电阻为100MΩm以上、并且高温加速寿命特性在200℃-20V/μm下为10000秒或超过10000秒的层合陶瓷电容器。另外，根据本发明，还可以得到用于具有上述特性的层合陶瓷电容器的电介质陶瓷。

Claims (2)

1、一种电介质陶瓷，其特征在于，以由(Bi0.5Na0.5)xBa1-xTiO3所表示的、x为0.05～0.2的具有钙钛矿结构的化合物为主成分，
作为第一副成分，相对于100mol所述主成分，含有以换算成1分子中1原子的氧化物计为0.25mol～1.50mol的选自Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb及Y中的至少1种稀土类金属、和以换算成1分子中1原子的氧化物计为0.2mol～1.50mol的Mg、和以换算成1分子中1原子的氧化物计为0.03mol～0.60mol的选自V、Cr及Mn中的至少1种金属，
作为第二副成分，含有SiO2或以SiO2为主体的玻璃成分。
2、一种层合陶瓷电容器，具有大致长方体形状的陶瓷层合体、和在该陶瓷层合体中间隔电介质陶瓷相对向且交替引出到不同的端面而形成的内部电极、和形成于所述陶瓷层合体的两端面上并与引出到该端面上的所述内部电极分别电连接的外部电极，其特征在于，
所述电介质陶瓷，以由(Bi0.5Na0.5)xBa1-xTiO3所表示的、x为0.05～0.2的具有钙钛矿结构的化合物为主成分，
作为第一副成分，相对于100mol所述主成分，含有以换算成1分子中1原子的氧化物计为0.25mol～1.5mol的选自Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb及Y中的至少1种稀土类金属、和以换算成1分子中1原子的氧化物计为0.2mol～1.5mol的Mg、和以换算成1分子中1原子的氧化物计为0.03mol～0.60mol的选自V、Cr及Mn中的至少1种金属，
作为第二副成分，含有SiO2或以SiO2为主体的玻璃成分，所述内部电极由Ni或Ni合金形成。
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CN102745984B (zh) * 2012-07-26 2014-08-27 陕西科技大学 一种高居里点无铅ptc陶瓷材料及其制备方法
CN105793938A (zh) * 2013-12-10 2016-07-20 株式会社村田制作所 层叠陶瓷电容器以及层叠陶瓷电容器的制造方法
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CN105390660A (zh) * 2015-10-27 2016-03-09 苏州攀特电陶科技股份有限公司 钛氧化物基陶瓷电极及其制备方法

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