CN109516803A - 一种超薄膜镍电极片式多层陶瓷电容器用y5v特性介质材料及其制备方法 - Google Patents

一种超薄膜镍电极片式多层陶瓷电容器用y5v特性介质材料及其制备方法 Download PDF

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CN109516803A
CN109516803A CN201811405406.2A CN201811405406A CN109516803A CN 109516803 A CN109516803 A CN 109516803A CN 201811405406 A CN201811405406 A CN 201811405406A CN 109516803 A CN109516803 A CN 109516803A
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multilayer ceramic
ceramic capacitor
dielectric material
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nickel electrode
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王孝国
刘艳丽
宋永生
张尹
沈才
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Guangdong Fenghua Advanced Tech Holding Co Ltd
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Abstract

本发明公开了一种超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料，按摩尔份计，包含主晶相90～98mol％、改性添加剂1.4～7.5mol％和烧结助熔剂0.5～8.0mol％，所述主晶相的结构式为(Ba1‑xCax)A(Ti1‑yZry)BO3，其中，0.01≤x≤0.05，0.10≤y≤0.25；1.003≤A/B≤1.10。本发明还公开了一种超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法，所述制备方法将BTZ与改性添加剂一同预烧合成，确保了改性添加剂能稳定分布在主晶相表面，不会出现局部成分偏离，提高超薄介质微观结构的连续性，进而提高MLCC器件的可靠性和介电性能稳定性。

Description

一种超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料 及其制备方法
技术领域
本发明涉及一种陶瓷材料及其制备方法，具体涉及一种超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料及其制备方法。
背景技术
MLCC用陶瓷粉料主要分为三大类(Y5V、X7R和COG)。其中Y5V(简称Y料)材料具有较高的介电常数、较稳定的温度特性，适用于容量范围广、稳定性要求不高的电路中，主要应用于隔直、耦合、旁路电路及对可靠性要求较高的中低频场合，如通信、计算机、汽车电子、数码家电等领域。
本体系瓷料一般采用选取钙钛矿结构的BaTi1-xZrxO3作主晶相，通过添加Ca2+、Mn2 +、Mg2+、Y3+等元素进行掺杂改性，制备出符合Ni电极Y5V材料特性的MLCC用陶瓷瓷料。
采用了湿化学法等液相合成技术制成的锆钛酸钡(BTZ)基础粉体，具有活性高，烧结温度低，晶粒均匀、细度适中、分散性好等优点，且非常容易地对粉体表面进行包裹和改性。通过引入抗还原剂、居里峰展宽剂、居里点移动剂、烧结助熔剂，制得高性能Ni电极MLCC用Y5V特性电子陶瓷材料FH-2FH143N。
但近年来由于环保限制，液相法制备BTZ被迫停止，因此，固相法势在必行。
发明内容
本发明的目的在于克服现有技术存在的不足之处而提供一种超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料及其制备方法。
为实现上述目的，本发明采取的技术方案为：一种超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料，按摩尔份计，包含主晶相90～98mol％、改性添加剂1.4～7.5mol％和烧结助熔剂0.5～8.0mol％，所述主晶相的结构式为(Ba1-xCax)A(Ti1-yZry)BO3，其中，0.01≤x≤0.05，0.10≤y≤0.25；1.003≤A/B≤1.10。
本发明所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料通过系统调节x、y、A/B值及改性添加剂的添加量，x、y、A/B值影响介电常数、损耗、居里点、容量温度系数和晶粒大小。通过发明人多次试验研究得出，当x、y、A/B值为上述范围时，可以移动系统的居里峰到室温25℃，既获得了常温下的高介电常数，获得了小的晶粒尺寸。
作为本发明所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的优选实施方式，所述改性添加剂包含Nb2O5、Mg(OH)2、CeO2、Y2O3和CaCO3中的至少一种；所述烧结助熔剂包含B2O3、SiO2、Bi2O3、MnO2和V2O5中的至少一种。
作为本发明所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的优选实施方式，在所述介质材料中，所述改性添加剂包含以下摩尔百分含量的组分：Nb2O5 0.1～0.5mol％、Mg(OH)2 0.1～0.5mol％、CeO2 0.1～0.5mol％、Y2O3 0.1～1.0mol％和CaCO3 1.0～5.0mol％。
改性添加剂选择上述配比的组分出于以下几点理由：
1、抗还原作用：因为镍内电极MLCC，为防止镍在烧结时氧化，因此要在还原气氛中烧结，在还原气氛下烧结，可以使Ti4+还原为Ti3+而使瓷体变黑并承半导体化，因此要引入Ca2+、Mg2、Y3+等离子抗还原；
2、移峰作用：由于钛酸钡的居里峰为120℃，需要加入以上离子把居里峰移至0至室温25℃附近；
3、展峰作用：将居里峰双肩展宽；
4、细化晶粒：Nb5+可以细化晶粒，又能作为施主，抑制Ti4+被还原。
通过添加上述改性添加剂，不但改善了瓷体的晶粒细化的问题和MLCC因介质做薄所引起的老化性能变差的问题，同时解决了瓷料抗还原问题。
作为本发明所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的优选实施方式，在所述介质材料中，所述烧结助熔剂包含以下摩尔百分含量的组分：B2O3 0～2mol％、SiO2 0.5～4mol％、Bi2O3 0～1mol％、MnO2 0～0.5mol％和V2O5 0～0.5mol％。
烧结助熔剂采用上述配比的组分可以：1、降低烧温；2、填充于晶粒间及晶粒内部气孔，减少气孔率，抑制晶粒过度长大，保持晶粒均匀；3、改善瓷体整体的致密度，进而改善材料耐压、老化等性能。
本发明的另一目的在于提供一种所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法，称取将主晶相、改性添加剂和烧结助熔剂原材料，进行湿法混合、分级研磨、喷雾干燥和预烧，得所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料。
本发明采用固相一次合成法替代液相法制备主晶相BTZ，由于国内普通原材料粗细程度不一，很难制备好主晶相BTZ，很难满足介质薄膜化的要求，本发明选取钙钛矿结构的BaTiO3基材料(Ba1-xCax)A(Ti1-yZry)BO3，以锆、钛、钡作为主材，但没有单独固相合成主晶相BaTi1-xZrxO3，而是与改性添加剂、烧结助熔剂一起一次合成，且经过球磨、砂磨工序进行预处理，使原材料在稳定性、均匀性、分散性和球形度方面大幅改进，在煅烧合成主晶相时，合成更稳定、球形度好。
主晶相材料、改性添加剂、烧结助熔剂共同烧结，能确保添加剂稳定分布在主晶相表面，不会出现局部成分偏离，再通过系统调节x、y、A/B、Zr/B值及添加剂的添加量，移动系统的居里峰到室温25℃，既获得了常温下的高介电常数(11000～15000(1KHZ,0.5V,20℃))，又能获得小尺寸的晶粒(≤4um)。
采用上述方法制得的产品达到液相法同样的介电性能，达到日本进口的超薄介质大容量瓷粉性能水平；解决了固相法合成粉体颗粒活性差和均匀性差的问题；大幅降低制造成本，生产成本低至30元/Kg。本发明制造的FH143NA瓷粉已供冠华分公司批量使用，钡钛比控制较液相法容易，性能优越、稳定。
作为本发明所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法的优选实施方式，所述原材料的比表面积为10±1m2/g。
当Y5V瓷料的介质层做得越薄时，对晶粒的细化及均匀性要求越高。介质层越薄，使介质层内单位面积的晶粒数越少，从而会导致可靠性下降。设计时通过添加纯度高、粒度细、分散性好的改性添加剂(Ca2+、Mg2+、Y3+等离子)，控制烧结过程中晶粒的生长，使其形成均匀的细晶，保证稳定的性能，从而满足Y5V的特性和实现材料的薄膜化。
作为本发明所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法的优选实施方式，所述原材料的D50小于650nm。采用上述粒径的原材料，可流延质量良好的<10um膜片。
作为本发明所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法的优选实施方式，所述原材料的D50小于500nm。
作为本发明所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法的优选实施方式，所述分级研磨为分别采用φ0.3mm和φ0.1mm的锆球进行分级研磨。
作为本发明所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法的优选实施方式，所述预烧的方法为：将干燥后的原料放入辊道窑或高温遂道长炉中由室温升温到高温区温度，再在高温区保温，最后降温到室温，所述升温过程是3～5小时，所述保温过程是2.5～5小时，所述室温是20±20℃，所述的高温区温度是1200±20℃。
作为本发明所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法的优选实施方式，所述预烧后还包括以下步骤：将预烧后的混合物进行二次湿法分散、分级研磨和喷雾干燥。
本发明的目的还在于提供一种所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的片式多层陶瓷电容器。
本发明的有益效果在于：本发明提供了一种超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料，本发明所述介质材料通过系统调节x、y、A/B值及改性添加剂的添加量，移动系统的居里峰到室温25℃，既获得了常温下的高介电常数，获得了小的晶粒尺寸。本发明还提供了一种超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法，所述制备方法不是单独合成BTZ，而是BTZ与添加剂一起一次预烧合成，确保了改性添加剂能稳定分布在主晶相表面，不会出现局部成分偏离，提高超薄介质微观结构的连续性，进而提高MLCC器件的可靠性和介电性能的稳定性。
附图说明
图1为实施例6所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料制备而成的片式多层陶瓷电容器介质层晶粒的扫描电镜图。
具体实施方式
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。
实施例1～12
实施例1～12为本发明所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的实施例，配方见表1。
实施例1～12所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料制备方法为：按表1中的实施例1～12的原料配方经湿法充分混合、选用φ0.3mm和φ0.1mm锆球分级研磨细化，用二流体喷雾塔喷雾脱水干燥后，放入辊道窑或高温遂道长炉中由室温升温到高温区温度，再在高温区保温，最后降温到室温,所述的升温过程是3～5小时，所述的保温过程是2.5～5小时，所述的室温是20±20℃，所述的高温区温度是1200±20℃。得到的混合材料，二次分散、研磨、干燥后得到分散性好的颗粒粒径在10～30um的介质材料。
表1实施例1～12所述介质材料的原料配方
表2实施例1～12的x、y、A/B、Zr/B值
组别 x y A/B
实施例1 0.01 0.10 1.003
实施例2 0.01 0.18 1.007
实施例3 0.01 0.25 1.10
实施例4 0.03 0.10 1.007
实施例5 0.03 0.18 1.10
实施例6 0.03 0.18 1.003
实施例7 0.05 0.10 1.10
实施例8 0.05 0.18 1.003
实施例9 0.05 0.25 1.10
实施例10 0.02 0.15 1.005
实施例11 0.05 0.185 1.006
实施例12 0.05 0.19 1.008
实施例1～12的介质材料经客户的MLCC制成，在还原气氛下1240℃烧结，其性能测试参数如表3所示。
表3实施例1～12所述介质材料性能
实施例 介电常数ε 损耗DF(％) 居里点(℃)
1 10500 3 0
2 11000 4 20
3 12000 5 25
4 15000 6 35
5 13000 5 25
6 12680 4 25
7 10000 3 10
8 9800 3 5
9 8000 3 -5
10 7500 2 -5
11 8500 5 -5
12 9000 6 -10
从表3可以看出，实施例1～12中，通过系统调节x、y和A/B值，可以使介质材料呈现不同的介电性能，三个变量相互影响，在本发明的x、y和A/B值范围的调控下，改性添加剂和烧结助熔剂尤其是在本发明范围内进行调控，能得到较好的性能。尤其是实施例6，当A/B＝1.003、Zr/B＝0.18时，介电常数适中，损耗较小，居里点在25℃，晶粒也最小，扫描电镜图见图1。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

1.一种超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料，其特征在于，按摩尔份计，包含主晶相90～98mol％、改性添加剂1.4～7.5mol％和烧结助熔剂0.5～8.0mol％，所述主晶相的结构式为(Ba1-xCax)A(Ti1-yZry)BO3，其中，0.01≤x≤0.05，0.10≤y≤0.25；1.003≤A/B≤1.10。
2.如权利要求1所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料，其特征在于，所述改性添加剂包含Nb2O5、Mg(OH)2、CeO2、Y2O3和CaCO3中的至少一种；所述烧结助熔剂包含B2O3、SiO2、Bi2O3、MnO2和V2O5中的至少一种。
3.如权利要求2所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料，其特征在于，在所述介质材料中，所述改性添加剂包含以下摩尔百分含量的组分：Nb2O5 0.1～0.5mol％、Mg(OH)2 0.1～0.5mol％、CeO2 0.1～0.5mol％、Y2O3 0.1～1.0mol％和CaCO3 1.0～5.0mol％。
4.如权利要求2所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料，其特征在于，在所述介质材料中，所述烧结助熔剂包含以下摩尔百分含量的组分：B2O3 0～2mol％、SiO2 0.5～4mol％、Bi2O3 0～1mol％、MnO2 0～0.5mol％和V2O5 0～0.5mol％。
5.一种如权利要求1～4中任一项所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法，其特征在于，称取将主晶相、改性添加剂和烧结助熔剂原材料，进行湿法混合、分级研磨、喷雾干燥和预烧，得所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料。
6.如权利要求5所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法，其特征在于，所述原材料的比表面积为10±1m2/g。
7.如权利要求5所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法，其特征在于，所述原材料的D50小于650nm；优选地，所述原材料的D50小于500nm。
8.如权利要求5所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法，其特征在于，所述预烧的方法为：将干燥后的原料放入辊道窑或高温遂道长炉中由室温升温到高温区温度，再在高温区保温，最后降温到室温，所述升温过程是3～5小时，所述保温过程是2.5～5小时，所述室温是20±20℃，所述的高温区温度是1200±20℃。
9.如权利要求5所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的制备方法，其特征在于，所述预烧后还包括以下步骤：将预烧后的混合物进行二次湿法分散、分级研磨和喷雾干燥。
10.一种包含权利要求1～4中任一项所述超薄膜镍电极片式多层陶瓷电容器用Y5V特性介质材料的片式多层陶瓷电容器。
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Application publication date: 20190326