CN106187166A - 一种用于中温烧结具有偏压特性的中高压瓷介电容器材料 - Google Patents

一种用于中温烧结具有偏压特性的中高压瓷介电容器材料 Download PDF

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CN106187166A
CN106187166A CN201610587358.8A CN201610587358A CN106187166A CN 106187166 A CN106187166 A CN 106187166A CN 201610587358 A CN201610587358 A CN 201610587358A CN 106187166 A CN106187166 A CN 106187166A
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CN106187166B (zh
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杨魁勇
程华容
宋蓓蓓
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Beijing Yuan Six Hongyuan Electronic Polytron Technologies Inc
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Abstract

本发明涉及一种用于中温烧结具有偏压特性的中高压瓷介电容器材料。其配方以质量份数计，含有：主料BaTiO3，100份；改性剂CaTiO3 2.5～4.5份、Nb2O5 1.0～1.8份、MnCO3 0.05～0.35份、CeO2 0～0.15份、SrCO3 0.05～0.35份、Co2O3 0.05～0.30份、MgO 0～0.08份、Sm2O3 0～0.20份、Y2O3 0～0.10份；烧结助剂2.5～4.0份，所述烧结助剂中含有ZnO、CaCO3、Li2CO3、H3BO3和SiO2中的三种或四种。本发明材料在保持高介电常数情况下，具有高击穿电压和偏压特性，适用于制备单层和多层瓷介电容器。

Description

一种用于中温烧结具有偏压特性的中高压瓷介电容器材料
技术领域
本发明属于电子信息材料与元器件技术领域，特别涉及一种用于中温烧结具有偏压特性的中高压瓷介电容器材料。
背景技术
随着电脑、通讯、航空航天、导弹等领域对击穿电压高、温度稳定性好、可靠性高的电容器的迫切需求，而普通X7R瓷料已经难以满足该类电容器的需求，能否开发并稳定生产击穿电压高、可靠性高的瓷料，成为当前急需解决的问题，这也是本专利解决的问题。
根据美国电子工业协会EIA标准，X7R型电容器陶瓷材料是以25℃的电容值为基准，在-55～+125℃的温度范围内，-15％≤ΔC/C0≤+15％，介质损耗≤2.5％。根据GJB192A-1998中规定偏压特性，以25℃时的电容量为基准，在-55℃～125℃范围内，施加额定直流偏压时，-25％≤ΔC/C0≤+15％。
目前常用作中高压陶瓷电容器的介质材料有三种，即钛酸钡系、钛酸锶系和反铁电介质陶瓷，其中后两种非铁电相材料体系均含铅，如钛酸锶系大多都掺杂钛酸铅以保障高介电常数，而反铁电体瓷主要是锆钛酸铅体系改性。通常，保持高介电常数需要材料具备强铁电性(如钛酸钡，属于典型的铁电体陶瓷)，而要保持高压则需高比例的非铁电相存在。通常钛酸钡体系烧结温度高于1300℃，添加烧结助剂可降低烧结温度，但烧结助剂的引入会降低体系的介电常数。
现已公开的涉及中高压瓷介电容器材料的文献很多，但能够同时兼顾无铅、中温烧结、高介电常数、X7R温度特性、偏压特性和高击穿电压的综合性能优异的瓷料，目前鲜见报道。
发明内容
针对现有技术不足，本发明提供了一种用于中温烧结具有偏压特性的中高压瓷介电容器材料。
一种用于中温烧结具有偏压特性的中高压瓷介电容器材料，其配方以质量份数计，含有：
主料BaTiO3 100份；
改性剂CaTiO3 2.5～4.5份、Nb2O5 1.0～1.8份、MnCO3 0.05～0.35份、Co2O3 0.05～0.30份、CeO2 0～0.15份、SrCO3 0～0.35份、MgO 0～0.08份、Sm2O3 0～0.25份、Y2O3 0～0.10份；
烧结助剂2.5～4.0份，所述烧结助剂中含有ZnO、CaCO3、Li2CO3、H3BO3和SiO2中的三种或四种。
以质量百分含量计，所述烧结助剂的配方为ZnO 55wt％～70wt％、CaCO3 0wt％～4wt％、Li2CO3 0wt％～5wt％、H3BO3 20wt％～35wt％、SiO2 6wt％～10wt％。
所述BaTiO3为四方相晶体结构，纯度≥99.8wt％，粒度D50为0.65～0.80μm。
一种用于中温烧结具有偏压特性的中高压瓷介电容器材料的制备方法，包括以下步骤：
S01：称量，按所设计的质量比例称取主料、改性剂和烧结助剂于球磨罐中，并加入合适比例的氧化锆球；
S02：球磨，以去离子水为介质进行混合球磨，球磨时间为5～8小时；
S03：烘干，温度为110℃～120℃，时间为6～8小时；
S04：粉碎过筛，研磨处理后，过100目筛，获得所述瓷介电容器材料。
所述CaTiO3的制备方法为：按照摩尔比1:1的比例称取CaCO3和TiO2，以去离子水为介质，球磨8小时；在120℃烘干，研磨处理后，过100目筛；在1060℃煅烧3小时，得到所述CaTiO3。
所述烧结助剂依次进行以下处理：
(1)称量：按照配方设计比例称取相应的原料于球磨罐中；
(2)球磨：球磨介质选用去离子水，球磨时间为6～8小时；
(3)烘干：温度为60℃～80℃，时间为12～16小时；
(4)粉碎过筛：对烘干后的块状料进行研磨破碎，过100目筛；
(5)煅烧：温度为540℃～850℃，时间为5～6小时，之后随炉自然冷却；
(6)研磨后再次球磨：将煅烧成块的烧结助剂研磨后，放入球磨罐，并加合适比例的锆球，以酒精为介质，球磨3～5小时；之后在60℃～80℃下烘干。
一种用于中温烧结具有偏压特性的中高压瓷介电容器材料制备电介质陶瓷的方法，包括以下步骤：
步骤1，将所述瓷介电容器材料进行造粒、压片，制成电介质陶瓷生坯；
步骤2，将上述步骤1中的电介质陶瓷生坯放入电阻炉中，以2～3℃/min由室温升高到500℃～600℃，保温2～3小时；
步骤3，再以4～6℃/min由500℃～600℃升至1130℃～1180℃，保温2～3小时；
步骤4，随炉冷却至室温，烧制成电介质陶瓷。
一种用于中温烧结具有偏压特性的中高压瓷介电容器材料在制备MLCC中的应用。
本发明的有益效果为：
本发明的用于中温烧结具有偏压特性的中高压瓷介电容器材料粒度分布均匀，分散性好，成型性工艺好，温度特性满足X7R要求，施加直流偏压2kv/mm时，-25％≤ΔC/C0≤+15％，室温相对介电常数为1900～2200，室温损耗≤1.5％，室温绝缘电阻率(2～5.5)×1013Ω·cm，击穿电压达17kv/mm，且不含Pb、Cd、Hg、Cr等有毒元素，在制备和使用过程中无污染，符合环保要求。
本发明的用于中温烧结具有偏压特性的中高压瓷介电容器材料在保持高介电常数情况下，具有高击穿电压和偏压特性是本发明的突出特色。
本发明的瓷介电容器材料具有优异的综合性能，且制备工艺简单，易于实现工业化生产，具有良好的产业化前景。
采用本发明的瓷介电容器材料制作的瓷介电容器能够实现中温烧结，并能够保持良好介电性能、较低的损耗、较高的绝缘电阻率和高击穿电压以及良好的温度稳定性和偏压特性。
本发明的瓷介电容器材料适用于单层和多层瓷介电容器，可用以开发中高压MLCC，也可用于生产对偏压特性有要求的MLCC产品。采用该材料生产的MLCC的平均击穿电压110kv/mm，最高可到120kv/mm。
具体实施方式
下面结合具体实施方式对本发明做进一步说明。应该强调的是，下述说明仅仅是示例性的，而不是为了限制本发明的范围及其应用。
本发明所选原料如无特殊说明，均可通过商业渠道采购。
实施例1
用于中温烧结具有偏压特性的中高压瓷介电容器材料，由主料、改性剂和烧结助剂构成。其中，主料为四方相晶体结构的BaTiO3，粒度D50＝0.65μm，纯度≥99.8wt％。
CaTiO3的制备：按照摩尔比1:1的比例称取CaCO3和TiO2，以去离子水为介质，球磨8小时；在120℃烘干，采用玛瑙研钵研磨处理后，过100目筛；在1060℃煅烧3小时，得到所述CaTiO3，用自封袋进行封装储存备用。
烧结助剂GF-1的制备：按照配方称取原料，其质量配比为22.7wt％H3BO3、68.2wt％ZnO和9.1wt％SiO2；选用去离子水作为球磨介质，球磨时间为6小时；在80℃下烘干，时间为12小时；采用玛瑙研钵研磨处理后，过100目筛；在570℃下煅烧，时间为5小时，之后随炉冷却；经过研磨后，放入球磨罐中，加入适量的锆球，以酒精为介质，再次球磨4小时，出料后，于80℃烘干，获得所述烧结助剂GF-1，并用自封袋进行封装储存备用。
瓷介电容器材料的制备：按照表1的重量比称取主料、改性剂和烧结助剂，以去离子水为介质，球磨混合8小时，在120℃下烘干8小时，取出瓷介电容器材料粉体，研磨并过100目筛后，用自封袋进行封装储存。
表1
对所制备的瓷介电容器材料进行性能考核：
电介质陶瓷的制备：称取3g瓷介电容器材料粉体，加入5wt％的PVA水溶液进行造粒，在200MPa下压制成Ф＝10mm的圆片，在空气中进行烧结，其烧结曲线为：由室温以2℃/min升至600℃，保温3小时；再以5℃/min升至目标温度，保温2.5小时，随炉自然冷却降至室温。
将烧制完的电介质陶瓷圆片的两表面涂覆银浆、烧制银电极，制成圆片电容器后测试容量值、损耗、绝缘电阻和击穿电压，并计算得出相对介电常数、绝缘电阻率和击穿场强；并测试其温度特性和偏压特性(施加直流偏压2kv/mm)特性，其电学性能参数见表2。
表2
采用配方4对应的陶瓷材料，经配料、流延成膜、印刷、叠层、匀压、排胶、烧结、倒角、涂端、烧端、电镀获得MLCC芯片(平均介质层厚度25μm)。MLCC电学性能如表3所示。
表3
实施例2
用于中温烧结具有偏压特性的中高压瓷介电容器材料，由主料、改性剂和烧结助剂构成。其中，主料为四方相晶体结构的BaTiO3，粒度D50＝0.75μm，纯度≥99.8wt％。
CaTiO3的制备：按照摩尔比1:1的比例称取CaCO3和TiO2，以去离子水为介质，球磨8小时；在120℃烘干，过100目筛；在1060℃煅烧3小时，得到所述CaTiO3。
烧结助剂GF-2的制备：按照配方称取原料，其质量配比为25.6wt％H3BO3、2.6wt％CaCO3、64.1wt％ZnO和7.7wt％SiO2；选用去离子水作为球磨介质，球磨时间为6小时；在80℃烘干，时间为12小时；采用玛瑙研钵研磨处理后，过100目筛；在850℃下煅烧，时间为5小时，之后随炉冷却；经过研磨后，放入球磨罐中，加入适量的锆球，以酒精为介质，再次球磨4小时，出料后，于80℃烘干，获得烧结助剂GF-2，并用自封袋封装储存。
瓷介电容器材料的制备：按照表4的重量比称取主料、改性剂和烧结助剂，以去离子水为介质球磨混合8小时，出料后，在120℃下烘干8小时，取出瓷介电容器材料粉体，研磨并过100目筛后，用自封袋封装。
表4
对所制备陶瓷材料进行性能考核：
电介质陶瓷的制备：称取3g陶瓷粉体，加入5wt％的PVA水溶液进行造粒，在200MPa下压制成Ф＝10mm的圆片，在空气中进行烧结，其烧结曲线为：由室温以2.0℃/min升至600℃，并保温3小时；再以5℃/min升至目标温度，保温2.5小时，随炉自然冷却降至室温。
将烧制完的电介质陶瓷圆片的两表面涂覆银浆、烧制银电极，制成圆片电容器后测试容量值、损耗、绝缘电阻和击穿电压，计算得出相对介电常数、绝缘电阻率和击穿场强；并测试其温度特性和偏压特性(施加直流偏压2kv/mm)特性，其电学性能参数见表5。
表5
采用配方7对应的瓷介电容器材料，经配料、流延、印刷、叠层、匀压、排胶、烧结、倒角、涂端、烧端、电镀获得MLCC芯片(平均介质层厚度25μm)。其电学性能如表6所示。
表6
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (8)

1.一种用于中温烧结具有偏压特性的中高压瓷介电容器材料，其特征在于，其配方以质量份数计，含有：
主料BaTiO3 100份；
改性剂CaTiO3 2.5～4.5份、Nb2O5 1.0～1.8份、MnCO3 0.05～0.35份、Co2O3 0.05～0.30份、CeO2 0～0.15份、SrCO3 0～0.35份、MgO 0～0.08份、Sm2O3 0～0.25份、Y2O3 0～0.10份；
烧结助剂2.5～4.0份，所述烧结助剂中含有ZnO、CaCO3、Li2CO3、H3BO3和SiO2中的三种或四种。
2.根据权利要求1所述一种用于中温烧结具有偏压特性的中高压瓷介电容器材料，其特征在于，以质量百分含量计，所述烧结助剂的配方为ZnO55wt％～70wt％、CaCO3 0wt％～4wt％、Li2CO3 0wt％～5wt％、H3BO3 20wt％～35wt％、SiO2 6wt％～10wt％。
3.根据权利要求1所述一种用于中温烧结具有偏压特性的中高压瓷介电容器材料，其特征在于，所述BaTiO3为四方相晶体结构，纯度≥99.8wt％，粒度D50为0.65～0.80μm。
4.权利要求1所述一种用于中温烧结具有偏压特性的中高压瓷介电容器材料的制备方法，其特征在于，包括以下步骤：
S01：称量，按所设计的质量比例称取主料、改性剂和烧结助剂于球磨罐中，并加入合适比例的氧化锆球；
S02：球磨，以去离子水为介质进行混合球磨，球磨时间为5～8小时；
S03：烘干，温度为110℃～120℃，时间为6～8小时；
S04：粉碎过筛，研磨处理后，过100目筛，获得所述瓷介电容器材料。
5.根据权利要求4所述的制备方法，其特征在于，所述CaTiO3的制备方法为：按照摩尔比1:1的比例称取CaCO3和TiO2，以去离子水为介质，球磨8小时；在120℃烘干，研磨处理后，过100目筛；在1060℃煅烧3小时，得到所述CaTiO3。
6.根据权利要求4所述的制备方法，其特征在于，所述烧结助剂依次进行以下处理：
(1)称量：按照配方设计比例称取相应的原料于球磨罐中；
(2)球磨：球磨介质选用去离子水，球磨时间为6～8小时；
(3)烘干：温度为60℃～80℃，时间为12～16小时；
(4)粉碎过筛：对烘干后的块状料进行研磨破碎，过100目筛；
(5)煅烧：温度为540℃～850℃，时间为5～6小时，之后随炉自然冷却；
(6)研磨后再次球磨：将煅烧成块的烧结助剂研磨后，放入球磨罐，并加合适比例的锆球，以酒精为介质，球磨3～5小时；之后在60℃～80℃下烘干。
7.权利要求1所述一种用于中温烧结具有偏压特性的中高压瓷介电容器材料制备电介质陶瓷的方法，其特征在于，包括以下步骤：
步骤1，将所述瓷介电容器材料进行造粒、压片，制成电介质陶瓷生坯；
步骤2，将上述步骤1中的电介质陶瓷生坯放入电阻炉中，以2～3℃/min由室温升高到500℃～600℃，保温2～3小时；
步骤3，再以4～6℃/min由500℃～600℃升至1130℃～1180℃，保温2～3小时；
步骤4，随炉冷却至室温，烧制成电介质陶瓷。
8.权利要求1所述一种用于中温烧结具有偏压特性的中高压瓷介电容器材料在制备MLCC中的应用。
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