CN114380591B - 一种介电陶瓷组合物制成的陶瓷电容器及制造方法 - Google Patents

一种介电陶瓷组合物制成的陶瓷电容器及制造方法 Download PDF

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CN114380591B
CN114380591B CN202011131356.0A CN202011131356A CN114380591B CN 114380591 B CN114380591 B CN 114380591B CN 202011131356 A CN202011131356 A CN 202011131356A CN 114380591 B CN114380591 B CN 114380591B
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裴钰
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Yuanliuhongyuan Suzhou Electronic Technology Co ltd
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Abstract

本发明公开了一种介电陶瓷组合物制成的陶瓷电容器及制造方法，包括基体粉末和基于基体粉末的辅助成分；包括以下步骤：A、首先对基体粉末和辅助成分分别进行研磨预分散，使D90＜1um，最终二者充分地混合研磨分散，达到(D90‑D10)/D50＜1，则辅助成分与基体粉末得到充分的分散与包覆，形成均匀完整的芯‑壳结构；B、采用空气气氛排塑初步制得多层陶瓷电容器，其中高温＜300℃，保温时间≥5h；C、采用N2‑H2‑H2O气氛对多层陶瓷电容器进行烧结，其中烧结最高温度控制在1220℃～1300℃，保温时间2h，然后降温至1100℃，保温时间≥2h。本发明具有超高常温与高温绝缘电阻，并在高温下保持超长寿命，能够应用于各种苛刻条件并确保产品性能的稳定与高可靠性。

Description

一种介电陶瓷组合物制成的陶瓷电容器及制造方法
技术领域
本发明涉及陶瓷电容器技术领域，具体是一种介电陶瓷组合物制成的陶瓷电容器及制造方法。
背景技术
近年来，随着电子器件在集成化、功能化、高可靠及低成本化方向发展，特别是未来5G智能时代的到来，以及军用领域的未来发展方向，多层陶瓷电容器的工作条件日趋严峻。因此迫切需要降低损耗、提高绝缘性，尤其是高温高压条件下的绝缘特性，以及提高其介电强度，保证其在各种复杂的环境条件下具有高可靠性与稳定性；同时多层陶瓷电容器持续向着大容量薄层化方向发展，对成本的要求也越来越甚。综上所述，亟待开发超高绝缘特性、低损耗、高介电常数的贱金属(如镍等)多层陶瓷电容器的介电组合物与多层陶瓷电容器。
目前市场上的镍电极技术的多层陶瓷电容器，大多数产品虽然在常温下保持较高的绝缘电阻，但是在高温下(≥125℃)或高压下，随着时间的增加，会出现绝缘电阻的急剧下降、漏电流指数级增加，从而导致产品的急剧发热、早期短路失效，无法满足高可靠产品的性能与寿命要求。这主要是因为使用镍电极技术的多层陶瓷电容器，一方面，为了防止镍电极的氧化，必须在还原气氛重烧结，而在还原气氛中烧结，现有的抗还原介电组合物和工艺，在产品内部仍然存在各种弱束缚的氧空位和电子等载流子，在高压及高温下，易获得能量而发生跃迁，形成导电粒子；另一方面，由于大容量薄层化，导致晶界阻挡的减少，导电粒子迁移的路径变短，因此，在温度升高时，被激发的导电粒子更易迁移至两端电极，从而导致漏电流的增加，出现产品绝缘电阻的降低而失效。而根据现有文献报道，CN1072831(叠层陶瓷电容器)尽管也具有相对较高的绝缘电阻，但是其高温寿命(15kV/mm，150℃)不超过230小时，综合性能依旧偏弱。
为了解决这些问题，需要发明一种合适的介电陶瓷组合物，并以合适的工艺实现材料的最佳性能，基于钛酸钡基介电材料的特性，必须在损耗、温度特性、绝缘性能、介电常数等方面综合平衡，探索最佳的镍电极的介电组合物配方与实现介电性能的最佳工艺。
发明内容
本发明的目的在于提供一种介电陶瓷组合物制成的陶瓷电容器及制造方法，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：
一种介电陶瓷组合物，包括基体粉末和基于基体粉末的辅助成分，所述基体粉末包含BamTiO3，其中0.995＜m＜1.030，且基体粉末的颗粒分布均匀，平均粒径≤300nm；所述辅助成分包含稀土氧化物、碱土金属氧化物或碳酸物、过渡金属氧化物、助烧结剂氧化物的组合物或玻璃化合物。
作为本发明再进一步的方案：所述基体粉末采用固相法、草酸盐法、水热法中的任意一种方法制得。
作为本发明再进一步的方案：所述稀土氧化物采用Y2O3、Ho2O3、Dy2O3、Gd2O3、Yb2O3、La2O3中的一种或两种，以100mol份的BamTiO3为基础，稀土氧化物的含量为0.2％～2.5％。
作为本发明再进一步的方案：所述碱土金属氧化物或碳酸物包含Ba、Ca、Mg等元素，以100mol份的BamTiO3为基础，碱土金属元素的含量为0.02％～3.5％。
作为本发明再进一步的方案：所述过渡金属氧化物采用Mo、V、W、Mn、Hf的氧化物或其它化合物形式等的一种或两种或三种或四种，以100mol份的BamTiO3为基础，过渡金属氧化物的含量为0.01％～1.5％。
作为本发明再进一步的方案：所述助烧结剂包含以硅为主成分的氧化物或玻璃组合物，采用SiO2、BaO、CaO、CuO等氧化物中的任意两种或两种以上，表现为x(BaO).y(CaO).z(CuO).t(SiO2)，其中0.02＜x＜0.6、0.02＜y＜0.5、0＜z＜0.2、0.3＜t＜1，且x+y+z+t＝1；以100mol份的BamTiO3为基础，助烧结剂的含量为0.5％～5％。
一种介电陶瓷组合物制成的陶瓷电容器，所述镍电极多层陶瓷电容器由上述材料作为电介质陶瓷层制成的。
一种介电陶瓷组合物制造陶瓷电容器的方法，包括以下步骤：
A、首先对基体粉末和辅助成分分别进行研磨预分散，使D90＜1um，最终二者充分地混合研磨分散，达到(D90-D10)/D50＜1，则辅助成分与基体粉末得到充分的分散与包覆，形成均匀完整的芯-壳结构；
B、采用空气气氛排塑初步制得多层陶瓷电容器，其中高温＜300℃，保温时间≥5h；
C、采用N2-H2-H2O气氛对多层陶瓷电容器进行烧结，其中烧结最高温度控制在1220℃～1300℃，保温时间2h，然后降温至1100℃，保温时间≥2h。
与现有技术相比，本发明的有益效果是：
当在室温25℃和125℃下进行测试，室温下的绝缘电阻为10000MΩ·uF或更高，125℃下绝缘电阻为1000MΩ·uF或更高；高温寿命(40kV/mm，140℃)可达1000小时或更高；温度特性符合EIA的X7R要求；产品的介电常数高达2500或更高，介电损耗≤2.5％或更低；另外即使在高温高湿度负荷下，它依然具有良好的耐候性。
与传统方案相比，本发明采取合适的陶瓷组合物，通过粉末特性的控制，合适的排塑和烧结工艺，得到了微观结构致密均匀、无分层裂纹的烧结体，从而实现产品的超高高绝缘电阻和优异的高温寿命；适合在各种苛刻条件下应用，减少终端产品因发热温升而导致失效的风险；尤其是航空航天及高精密电子控制器件要求的领域，保证产品性能的稳定与高可靠性。
附图说明
图1为本发明中粉末形貌的微观结构示意图；
图2为本发明中烧结瓷体的微观结构示意图；
图3为本发明中多层陶瓷电容器的结构示意图。
具体实施方式
请参阅图1～3，本发明实施例中，
一种介电陶瓷组合物，包括基体粉末和基于基体粉末的辅助成分；
基体粉末是BamTiO3，其中0.995＜m＜1.030，且基体粉末的颗粒分布均匀，平均粒径≤300nm；采用固相法、草酸盐法、水热法中的任意一种方法制得；
辅助成分包含稀土氧化物、碱土金属氧化物或碳酸物、过渡金属氧化物、助烧结剂氧化物的组合物或玻璃化合物，具体如下：
稀土氧化物采用Y2O3、Ho2O3、Dy2O3、Gd2O3、Yb2O3、La2O3中的一种或两种，以100mol份的BamTiO3为基础，稀土氧化物的含量为0.2％～2.5％；
碱土金属氧化物或碳酸物包含Ba、Ca、Mg等元素，以100mol份的BamTiO3为基础，碱土金属元素的含量为0.02％～3.5％；
过渡金属氧化物采用Mo、V、W、Mn、Hf的氧化物或其它化合物形式等的一种或两种或三种或四种，以100mol份的BamTiO3为基础，过渡金属氧化物的含量为0.01％～1.5％；
助烧结剂包含以硅为主成分的氧化物或玻璃组合物，采用SiO2、BaO、CaO、CuO等氧化物中的任意两种或两种以上，表现为x(BaO).y(CaO).z(CuO).t(SiO2)，其中0.02＜x＜0.6、0.02＜y＜0.5、0＜z＜0.2、0.3＜t＜1，且x+y+z+t＝1；以100mol份的BamTiO3为基础，助烧结剂的含量为0.5％～5％。
上述各组分的作用及注意事项如下：
稀土氧化物，提高产品的高温寿命和可靠性，同时提升产品的容量温度特性，但是含量过高，会使产品难以烧结，导致产品绝缘性能下降；碱土金属氧化物，改善产品的烧结性能和绝缘性能，尤其是Mg元素，抑制晶粒成长，形成芯-壳结构，但含量过多，会导致温度特性以及介电常数的下降；过渡金属氧化物，提高产品的抗还原性，保证产品的高温绝缘性能，但是含量过高，会使绝缘性能和容量的温度特性变差。助烧结剂的作用是降低陶瓷的烧结温度，减少内部应力，同时形成晶界势垒，提高产品的可靠性，但是含量过高，会使产品的强度变差，介电常数下降。
一种介电陶瓷组合物制成的陶瓷电容器，镍电极多层陶瓷电容器由上述材料作为电介质陶瓷层制成的。
一种介电陶瓷组合物制造陶瓷电容器的方法，包括以下步骤：
A、准备好满足上述条件的介电组合物，现将基体粉末和辅助成分进行预分散，其过程为：先加入溶剂(酒精、甲苯)与分散剂，使用钇稳定氧化锆球进行研磨，使得基体粉末和辅助成分充分分散，并控制粉体的颗粒粒径分布D90＜1.00um、(D90-D10)/D50＜1.0，保证粉末颗粒进行充分的个体分散，并使辅助成分充分地弥散在基体粉末的颗粒表面，这样保证在烧结过程中形成完整芯-壳结构；然后加入粘合剂与塑化剂，使用高速搅拌机或砂磨机使粘合剂分散均匀，再利用流延机流延得到具有一定的强度与韧性，和目标厚度的膜片；随后通过在膜片上印刷设计要求的镍内电极图案，最后通过叠层、匀压、切割得到预期设计的生胚产品；
B、对生胚产品通过排塑工序，使其中的粘合剂等有机物充分地烧出，同时要保证产品的完整性，不能因为燃烧或裂解过于剧烈而使产品开裂，因此要根据有机物的裂解反应曲线，同时考虑镍电极的氧化特性，结合设备特点，制定相应的排塑程序；本发明使用空气排塑，最高温度＜300℃，保温时间≥5h，最终使产品中的残炭含量＜1.8％，甚至＜0.1％，从而避免局部残炭的存在，影响产品烧结的均匀性与致密性；
C、将排塑完的产品在含有N2/H2/H2O混合气氛的烧结炉中进行烧结，具体流程如下：
①氧分压控制在10-12～10-9MPa的还原性气氛，烧结温度控制在1260～1290℃，保温2h，对产品进行烧结；然后降温到1100℃，控制氧含量在10～50PPM，保持3～5h，对产品进行再氧化处理，对因还原气氛烧结而产生的氧空位进行补氧处理，最终得到烧结致密、晶粒细密且分布均匀的高绝缘性陶瓷体；
②对烧结致密的陶瓷体的左右两端进行倒角处理，然后在左右两端涂覆外电极Cu电极浆，并在800～880℃的N2/Air气氛下进行铜端子烧结，最后再电镀上阻挡层镍电极和可焊层Sn，即制备出完整的多层陶瓷器产品。
通过上述要求与过程制备出的产品可满足EIA标准的X5R(工作温度：-55℃～85℃)和X7R(工作温度：-55℃～125℃特性)，同时室温绝缘电阻与125℃绝缘电阻(测试条件：16V，60s)，可达10000MΩ·uF和1000MΩ·uF或更高，而且高加速寿命(400V，140℃)可达100小时或更高；
测试叠层陶瓷电容器电性能的条件如下：
用自动桥式测量仪，在1KHz的频率，1Vrms及20℃测定电容量(C)和介电损耗(tanδ)，由测得的静电容量计算出介电常数(ε)。
在25℃和125℃，产品在各温度下保温至少30min，然后将16V的直流电压施加于各样品60s，用绝缘电阻测定仪，测定绝缘电阻(R)，由静电容量(C)和绝缘电阻(R)计算不同温度下和电压下的RC积。
静电容量随温度的变化率(容量的温度特性)，以ΔC/C25℃表示，表示相对于25℃时的静电容量在-55℃～125℃之间的变化率。
高加速寿命测试：每次取15支样品，在140℃，施加40kV/mm的直流电压，测定其绝缘电阻随时间的变化率，以测定其高温高压下的高加速寿命。各样品的绝缘电阻(R)达到低于RC＜30MΩ·uF的时间，即为寿命，结果以平均寿命表示。
所实验实例测试结果与比较例子结果：
下表实例使用草酸盐法的BamTiO3粉末，平均颗粒大小约300nm，m约为0.997实例中，各组分含量使以BamTiO3为100mol份为基础的比例添加。
注：1～5为实施例样品编号，*为比较例，RC绝缘电阻较低，高加速寿命相对偏低。
以上所述的，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (4)

1.一种介电陶瓷组合物，包括基体粉末和基于基体粉末的辅助成分，其特征在于，所述基体粉末包含BamTiO3，其中m为0.997，且基体粉末的颗粒分布均匀，平均粒径为300nm；所述辅助成分为稀土氧化物、碱土金属碳酸物、过渡金属氧化物、助烧结剂玻璃组合物；
所述稀土氧化物为Y2O3和Gd2O3，以100mol份的BamTiO3为基础，稀土氧化物的含量为1.50％Y2O3和0.20％Gd2O3；
所述碱土金属碳酸物为BaCO3、CaCO3和MgCO3，以100mol份的BamTiO3为基础，碱土金属碳酸物的含量为1.20％BaCO3、0.60％CaCO3和0.40％MgCO3；
所述过渡金属氧化物为WO3、Mo3O4和V2O5，以100mol份的BamTiO3为基础，过渡金属氧化物的含量为0.15％WO3、0.60％Mo3O4和0.10％V2O5；
所述玻璃组合物为0.35(BaO)0.2(CaO)0.05(CuO)0.4(SiO2)；以100mol份的BamTiO3为基础，助烧结剂的含量为2.00％。
2.根据权利要求1所述的一种介电陶瓷组合物，其特征在于，所述基体粉末采用固相法、草酸盐法、水热法中的任意一种方法制得。
3.根据权利要求1或2所述的一种介电陶瓷组合物制成的陶瓷电容器，其特征在于，所述陶瓷电容器为镍电极多层陶瓷电容器，由上述材料作为电介质陶瓷层制成的。
4.根据权利要求1或2所述的一种介电陶瓷组合物制成的陶瓷电容器的方法，其特征在于，包括以下步骤：
A、首先对基体粉末和辅助成分分别进行研磨预分散，使D90＜1μm，最终二者充分地混合研磨分散，达到(D90-D10)/D50＜1，则辅助成分与基体粉末得到充分的分散与包覆，形成均匀完整的芯-壳结构；
B、采用空气气氛排塑初步制得多层陶瓷电容器，其中高温＜300℃，保温时间≥5h；
C、采用N2-H2-H2O气氛对多层陶瓷电容器进行烧结，其中烧结最高温度控制在1220℃～1300℃，保温时间2h，然后降温至1100℃，保温时间≥2h。
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