CN111410527B - 一种复相巨介电陶瓷材料及其制备方法 - Google Patents

一种复相巨介电陶瓷材料及其制备方法 Download PDF

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CN111410527B
CN111410527B CN202010205096.0A CN202010205096A CN111410527B CN 111410527 B CN111410527 B CN 111410527B CN 202010205096 A CN202010205096 A CN 202010205096A CN 111410527 B CN111410527 B CN 111410527B
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ceramic material
dielectric ceramic
complex phase
giant dielectric
giant
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CN111410527A (zh
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曹秀华
刘建梅
陈德宏
任海东
刘芸
特里·詹姆士·弗朗科姆
付振晓
沓世我
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Guangdong Fenghua Advanced Tech Holding Co Ltd
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Guangdong Fenghua Advanced Tech Holding Co Ltd
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Priority to CN202010205096.0A priority Critical patent/CN111410527B/zh
Priority to PCT/CN2020/081953 priority patent/WO2021184414A1/zh
Priority to US17/296,259 priority patent/US20220127197A1/en
Priority to JP2021527997A priority patent/JP7333146B2/ja
Priority to KR1020217015098A priority patent/KR102607584B1/ko
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Abstract

本发明公开了一种复相巨介电陶瓷材料，所述复相巨介电陶瓷材料的总组分表达式为AxBnxTi1‑(n+1)xO2；其中，A选自Nb、Ta、V、Mo、Sb中的至少一种，B选自In、Ga、Al、Co、Cr、Sc、Fe(III)、三价稀土阳离子中的至少一种；n为B与A的摩尔比，1<n≤5，0<x≤0.1。本申请所制备的复相巨介电陶瓷材料在具有巨介电﹑低损耗﹑频率和温度稳定性好的优良性能的基础上，重点突出其具有高绝缘电阻率的抗高压击穿性能，其绝缘电阻率高于1011Ωcm，可应用于高能存储器件和超级电容器。同时，本发明还公开一种所述复相巨介电陶瓷材料的制备方法。

Description

一种复相巨介电陶瓷材料及其制备方法
技术领域
本发明涉及一种复相巨介电陶瓷材料及其制备方法。
背景技术
高能存储器件﹑超级电容器和设备小型化的研究表明，作为其中必不可少的介电材料，需同时具备巨介电、低损耗、优良的温度和频率稳定性及优良的抗高压击穿能力。器件能量存储能力与所用介电材料的工作电压的平方成正比，由此可见，研究介电陶瓷材料抗击穿性能的必要性。
众多研究表明，铁电材料，如BaTiO3，满足高介电常数要求，但是其介电常数随温度变化非常大；其他非铁电材料，如CaCuTi3O12(CCTO)﹑掺杂NiO和La2xSrxNiO4(x＝1/3、1/8)等，介电常数在较宽温度范围内可达105以上，但是介电损耗很高(>0.1)。
基于此，需要制备一种同时具有高介电常数﹑低损耗﹑温度和频率稳定性好及优良抗高压击穿性能的介电陶瓷材料。
发明内容
基于此，本发明的目的在于克服上述现有技术的不足之处而提供一种复相巨介电陶瓷材料。
为实现上述目的，本发明所采取的技术方案为：一种复相巨介电陶瓷材料，所述复相巨介电陶瓷材料的总组分表达式为AxBnxTi1-(n+1)xO2；其中，A选自Nb、Ta、V、Mo、Sb中的至少一种，B选自In、Ga、Al、Co、Cr、Sc、Fe(III)、三价稀土阳离子中的至少一种；n为B与A的摩尔比，1<n≤5，0<x≤0.1。
本申请所制备的复相巨介电陶瓷材料在具有巨介电﹑低损耗﹑频率和温度稳定性好的优良性能的基础上，重点突出其具有高绝缘电阻率的抗高压击穿性能，其绝缘电阻率高于1011Ωcm，可应用于高能存储器件和超级电容器。
优选地，所述复相巨介电陶瓷材料的主相为A5+与B3+共掺杂的金红石二氧化钛，副相为B2TiO5,且副相均匀分散于主相中。主相提供巨介电性能，副性具有极其优良的电绝缘性能；非连续、均匀分布在主相晶界处的副相能有效阻断弱束缚电荷的传输，从而大大提高材料的工作电压，击穿电压，并不恶化巨介电性能。
更优选地，所述副相为正交结构的B2TiO5。所述副相为在一次性合成过程中具有与主相相比，相对较低的合成温度，从而可自动相分离的正交结构的B2TiO5。
优选地，所述复相巨介电陶瓷材料的电阻率大于1011Ωcm。
优选地，所述复相巨介电陶瓷材料在20Hz到2×106Hz频率范围内的介电常数大于10000；同时，所述复相巨介电陶瓷材料在频率低于2×105Hz时，介电损耗小于0.05。
优选地，所述复相巨介电陶瓷材料在-160℃到170℃温度范围内的介电常数大于10000；同时，所述复相巨介电陶瓷材料在-50℃到150℃温度范围内，介电损耗小于0.05。
同时，本发明还提供一种所述的复相巨介电陶瓷材料的制备方法，包括如下步骤：
(1)依照复相巨介电陶瓷材料的总组分表达式AxBnxTi1-(n+1)xO2，称取相应的钛源、A源和B源；
(2)将上述反应物置于球磨罐中，球磨、干燥，得到均一混合物粉体；
(3)将步骤(2)所得混合物粉体置于研钵中，加入占所述混合物粉体重量的5％～10％的纯净水，混合均匀；然后将粉体置入模具中，在至少400MPa压力下保压，得到生片；将生片置于研钵中，粉碎研磨，得到预备粉体；
(4)将步骤(3)所得的预备粉体置入模具中，在至少2MPa压力下保压成型，然后烧结处理；具体烧结工艺为：升温速率为1.5-15℃/min，温度范围为1200℃～1500℃，保温时间为1～24小时；结束后，自然冷却至室温，得到致密的陶瓷片；
(5)将步骤(4)所得的陶瓷片进行表面抛光处理，然后进行退火；具体退火工艺为：升温速率为1.5-15℃/min，温度范围为1000℃～1200℃，保温时间为1～24小时；结束后，自然冷却至室温，得到复相巨介电陶瓷材料。
优选地，所述步骤(1)中，钛源为TiO2，A源为A2O5，B源选自B2O3﹑B2(C2O4)3﹑B2(C2O4)3的水合物﹑B(NO3)3﹑B(NO3)3的水合物﹑B2(SO4)3﹑B2(SO4)3的水合物﹑B2(CO3)3﹑B2(CO3)3的水合物﹑B(C2H3O2)3、B(C2H3O2)3的水合物中的至少一种。非氧化物B源有助于进一步降低副相的合成温度和在晶界的蛹动性,形成B相的非连续，均匀分布。
优选地，所述步骤(2)中的球磨为：以乙醇或丙酮为分散剂，钇稳定的氧化锆球为球磨介质，球磨12小时以上；所述步骤(4)和步骤(5)中，烧结和退火的气氛为空气。
优选地，所述步骤(5)中，表面抛光的工艺为：先用240目的砂纸进行粗抛，后用1200目的砂纸进行细抛；这样可以形成光滑表面，避免表面粗糙度对样品退火后性能的影响。
相对于现有技术，本发明的有益效果为：
本发明通过同时掺杂A5+和B3+金属离子进行化学修饰金红石二氧化钛结构，得到主相为A5+和B3+共掺杂的金红石二氧化钛、且副相(B2TiO5)均匀分散于其中的复相材料；使之体现巨介电﹑低损耗﹑频率和温度稳定性好的优良性能的基础上，重点突出其具有高绝缘电阻率的抗高压击穿性能，可应用于高能存储器件和超级电容器；其优点具有体现为以下三方面：
(1)复相巨介电陶瓷材料的主相为A5+与B3+共掺杂的金红石二氧化钛，副相为B2TiO5，且副相均匀分散于主相中；
(2)该复相巨介电陶瓷材料具有高绝缘电阻率的抗高压击穿能力，其电阻率≥1011Ωcm；
(3)在20Hz到2×106Hz频率范围内和-160℃到170℃温度范围内，其介电常数(>104)具有极小的频率和温度依赖性；同时频率低于2×105Hz，温度范围为-50℃到150℃时，其介电损耗小于0.05。
附图说明
图1为实施例1和实施例2制备的复相巨介电陶瓷材料的XRD图谱；
图2为实施例1和实施例2制备的复相巨介电陶瓷材料的背散射电子(BSE)图片和相应的二次电子(SE)图片；
图3为实施例1所制备的复相巨介电陶瓷材料在室温下，其介电常数和介电损耗与频率的关系图谱；
图4为实施例1所制备的复相巨介电陶瓷材料，在选定的4个频率(100Hz﹑1KHz﹑10KHz和100KHz)下，其介电常数和介电损耗与温度的关系图谱；
图5为实施例2制备的复相巨介电陶瓷材料的背散射电子(BSE)图片。
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，下面将结合附图和具体实施例对本发明作进一步说明。
实施例1
本发明所述复相巨介电陶瓷材料的一种实施例，本实施例所述复相巨介电陶瓷材料的总组分表达式为AxBnxTi1-(n+1)xO2，其中A为Nb，B为In，x＝0.0125，n＝2。
本实施例所述复相巨介电陶瓷材料的制备方法如下：
(1)称取0.2492g Nb2O5﹑0.5206g In2O3和11.5312g TiO2；
(2)将上述反应物置于球磨罐中，以乙醇或丙酮为分散剂，钇稳定的氧化锆球为球磨介质，球磨12小时以上，混合均匀；干燥后，得均一混合物粉体；
(3)步骤(2)所得混合物粉体进行造粒处理，具体造粒工艺如下：混合粉体置于研钵中，加入占混合物粉体重量的5％的纯净水，混合均匀；然后将粉体置入32mm模具中，在416MPa压力下保压，得到生片；将前述生片置于研钵中，粉碎研磨，得到预备粉体；
(4)将步骤(3)所得的预备粉体置入1.2mm模具中，在2MPa压力下保压成型，然后在空气中进行烧结，具体烧结工艺如下：升温速率为15℃/min，温度范围为1420℃，保温时间为3小时，结束后，自然冷却至室温，得到致密的陶瓷片；
(5)将步骤(4)所得的陶瓷片先后用240目和1200目的砂纸进行表面抛光处理，然后在空气中进行退火，具体退火工艺如下：升温速率为15℃/min，温度范围为1200℃，保温时间为1小时，结束后，自然冷却至室温，得到最终复相巨介电陶瓷材料。
实施例2
本发明所述复相巨介电陶瓷材料的一种实施例，本实施例所述复相巨介电陶瓷材料的总组分表达式为AxBnxTi1-(n+1)xO2，其中A为Nb，B为In，x＝0.075，n＝2。
本实施例所述复相巨介电陶瓷材料的制备方法如下：
(1)称取1.4952g Nb2O5﹑3.1233g In2O3和9.2849g TiO2；
(2)将上述反应物置于球磨罐中，以乙醇或丙酮为分散剂，钇稳定的氧化锆球为球磨介质，球磨12小时以上，混合均匀；干燥后，得均一混合物粉体；
(3)步骤(2)所得混合物粉体进行造粒处理，具体造粒工艺如下：混合粉体置于研钵中，加入占混合物粉体重量的10％的纯净水，混合均匀；然后将粉体置入32mm模具中，在416MPa压力下保压，得到生片；将前述生片置于研钵中，粉碎研磨，得到预备粉体；
(4)将步骤(3)所得的预备粉体置入1.2mm模具中，在2MPa压力下保压成型，然后在空气中进行烧结，具体烧结工艺如下：升温速率为3.8℃/min，温度范围为1200℃，保温时间为24小时，结束后，自然冷却至室温，得到致密的陶瓷片；
(5)将步骤(4)所得的陶瓷片先后用240目和1200目的砂纸进行表面抛光处理，然后在空气中进行退火，具体退火工艺如下：升温速率为5℃/min，温度范围为1000℃，保温时间为24小时，结束后，自然冷却至室温，得到最终复相巨介电陶瓷材料。
实施例3
本发明所述复相巨介电陶瓷材料的一种实施例，本实施例所述复相巨介电陶瓷材料的总组分表达式为AxBnxTi1-(n+1)xO2，其中A为Nb，B为In，x＝0.0125，n＝3。
本实施例所述复相巨介电陶瓷材料的制备方法如下：
(1)称取0.2492g Nb2O5﹑0.7809g In2O3和11.3809g TiO2；
(2)将上述反应物置于球磨罐中，以乙醇或丙酮为分散剂，钇稳定的氧化锆球为球磨介质，球磨12小时以上，混合均匀；干燥后，得均一混合物粉体；
(3)步骤(2)所得混合物粉体进行造粒处理，具体造粒工艺如下：混合粉体置于研钵中，加入占混合物粉体重量的5％的纯净水，混合均匀；然后将粉体置入32mm模具中，在416MPa压力下保压，得到生片；将前述生片置于研钵中，粉碎研磨，得到预备粉体；
(4)将步骤(3)所得的预备粉体置入1.2mm模具中，在2MPa压力下保压成型，然后在空气中进行烧结，具体烧结工艺如下：升温速率为3.8℃/min，温度范围为1420℃，保温时间为3小时，结束后，自然冷却至室温，得到致密的陶瓷片；
(5)将步骤(4)所得的陶瓷片先后用240目和1200目的砂纸进行表面抛光处理，然后在空气中进行退火，具体退火工艺如下：升温速率为5℃/min，温度范围为1200℃，保温时间为1小时，结束后，自然冷却至室温，得到最终复相巨介电陶瓷材料。
实施例4
本发明所述复相巨介电陶瓷材料的一种实施例，本实施例所述复相巨介电陶瓷材料的总组分表达式为AxBnxTi1-(n+1)xO2，其中A为Nb，B为In，x＝0.0125，n＝4。
本实施例所述复相巨介电陶瓷材料的制备方法如下：
(1)称取0.2492g Nb2O5﹑1.0412g In2O3和11.2312g TiO2；
(2)将上述反应物置于球磨罐中，以乙醇或丙酮为分散剂，钇稳定的氧化锆球为球磨介质，球磨12小时以上，混合均匀；干燥后，得均一混合物粉体；
(3)步骤(2)所得混合物粉体进行造粒处理，具体造粒工艺如下：混合粉体置于研钵中，加入占混合物粉体重量的5％的纯净水，混合均匀；然后将粉体置入32mm模具中，在416MPa压力下保压，得到生片；将前述生片置于研钵中，粉碎研磨，得到预备粉体；
(4)将步骤(3)所得的预备粉体置入1.2mm模具中，在2MPa压力下保压成型，然后在空气中进行烧结，具体烧结工艺如下：升温速率为3.8℃/min，温度范围为1420℃，保温时间为3小时，结束后，自然冷却至室温，得到致密的陶瓷片；
(5)将步骤(4)所得的陶瓷片先后用240目和1200目的砂纸进行表面抛光处理，然后在空气中进行退火，具体退火工艺如下：升温速率为5℃/min，温度范围为1200℃，保温时间为1小时，结束后，自然冷却至室温，得到最终复相巨介电陶瓷材料。
请参阅图1，图1为实施例1(1.25at.％Nb5++2.5at.％In3+)和实施例2
(7.5at.％Nb5++15at.％In3+)制备的复相巨介电陶瓷材料的XRD图谱。从图1可以看出，实施例1和实施例2制备的材料同时具有金红石二氧化钛和正交In2TiO5两种结构。
请参阅图2，图2为实施例1(1.25at.％Nb5++2.5at.％In3+)和实施例2
(7.5at.％Nb5++15at.％In3+)制备的复相巨介电陶瓷材料的背散射电子(BSE)图片和相应的二次电子(SE)图片。图2可以进一步证明：实施例1和实施例2制备的材料具有两种物相，且副相均匀分散于主相中。
请参阅图3，图3为实施例1(1.25at.％Nb5++2.5at.％In3+)所制备的陶瓷材料在室温下，其介电常数和介电损耗与频率的关系图谱。从图3可以看出，在20Hz到2×106Hz频率范围内，实施例1(1.25at.％Nb5++2.5at.％In3+)制备的陶瓷材料的介电常数大于10000，且具有极小的频率依赖性，同时频率低于2×105Hz时，其介电损耗小于0.05。
请参阅图4，图4为实施例1(1.25at.％Nb5++2.5at.％In3+)所制备的陶瓷材料，在选定的4个频率(100Hz﹑1KHz﹑10KHz和100KHz)下，其介电常数和介电损耗与温度的关系图谱。从图4可以看出，在-160℃到170℃温度范围内，实施例1(1.25at.％Nb5++2.5at.％In3+)制备的陶瓷材料的介电常数大于10000，且具有极小的温度依赖性，同时在-50℃到150℃温度范围内，其介电损耗小于0.05。
请参阅图5和表1，图5为实施例2(7.5at.％Nb5++15at.％In3+)材料的背散射电子(BSE)图片，表1为图5所示点的能量散射图谱(EDS)的组分分析，具体如下：
表1图5所示点的能量散射图谱(EDS)的组分分析
EDS# Ti at.％ Nb at.％ In at.％
1 83.30 8.25 8.46
2 82.92 8.38 8.69
3 32.93 0.98 66.09
结合图1、图5和表1，可以进一步表明，所制备的复相巨介电陶瓷材料的主相为Nb5+与In3+共掺杂的金红石二氧化钛，副相为B2TiO5。
请参阅表2，表2总结了实施例1、实施例3、实施例4和参考组分的电阻率、介电常数和介电损耗，具体如下：
表2实施例1、实施例3、实施例4和参考组分的电阻率、介电常数和介电损耗
Figure BDA0002419652330000081
对比参考组分(1.25at％Nb5++1.25at％In3+)，实施例1、实施例3和实施例4具有更高的电阻率，并且同时具有高介电常数(>10000)和低介电损耗(<0.05)，由此表明：非连续、均匀分布在主相晶界处的副相有效阻断弱束缚电荷的传输，提高材料的工作电压，击穿电压，并不恶化巨介电性能。
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 (8)

1.一种复相巨介电陶瓷材料，其特征在于，所述复相巨介电陶瓷材料的总组分表达式为AxBnxTi1-(n+1)xO2；其中，A选自Nb、Ta、V、Mo、Sb中的至少一种，B选自In、Ga、Al、Co、Cr、Sc、Fe(III)、三价稀土阳离子中的至少一种；
n为B与A的摩尔比，1<n≤5，0<x≤0.1；
所述复相巨介电陶瓷材料的主相为A5+与B3+共掺杂的金红石二氧化钛，副相为B2TiO5，且副相均匀分散于主相中；
所述复相巨介电陶瓷材料的制备方法包括如下步骤：
(1)依照复相巨介电陶瓷材料的总组分表达式AxBnxTi1-(n+1)xO2，称取相应的钛源、A源和B源；
(2)将上述反应物置于球磨罐中，球磨、干燥，得到均一混合物粉体；
(3)将步骤(2)所得混合物粉体置于研钵中，加入占所述混合物粉体重量的5％～10％的纯净水，混合均匀；然后将粉体置入模具中，在至少400MPa压力下保压，得到生片；将生片置于研钵中，粉碎研磨，得到预备粉体；
(4)将步骤(3)所得的预备粉体置入模具中，在至少2MPa压力下保压成型，然后烧结处理；具体烧结工艺为：升温速率为1.5-15℃/min，温度范围为1200℃～1500℃，保温时间为1～24小时；结束后，自然冷却至室温，得到致密的陶瓷片；
(5)将步骤(4)所得的陶瓷片进行表面抛光处理，然后进行退火；具体退火工艺为：升温速率为1.5-15℃/min，温度范围为1000℃～1200℃，保温时间为1～24小时；结束后，自然冷却至室温，得到复相巨介电陶瓷材料。
2.如权利要求1所述的复相巨介电陶瓷材料，其特征在于，所述副相为正交结构的B2TiO5。
3.如权利要求1～2任一项所述的复相巨介电陶瓷材料，其特征在于，所述复相巨介电陶瓷材料的电阻率大于1011Ω· cm。
4.如权利要求1～2任一项所述的复相巨介电陶瓷材料，其特征在于，所述复相巨介电陶瓷材料在20Hz到2×106Hz频率范围内的介电常数大于10000；同时，所述复相巨介电陶瓷材料在频率低于2×105Hz时，介电损耗小于0.05。
5.如权利要求1～2任一项所述的复相巨介电陶瓷材料，其特征在于，所述复相巨介电陶瓷材料在-160℃到170℃温度范围内的介电常数大于10000；同时，所述复相巨介电陶瓷材料在-50℃到150℃温度范围内，介电损耗小于0.05。
6.如权利要求1所述的复相巨介电陶瓷材料，其特征在于，所述步骤(1)中，钛源为TiO2，A源为A2O5，B源选自B2O3﹑B2(C2O4)3﹑B2(C2O4)3的水合物﹑B(NO3)3﹑B(NO3)3的水合物﹑B2(SO4)3﹑B2(SO4)3的水合物﹑B2(CO3)3﹑B2(CO3)3的水合物﹑B(C2H3O2)3、B(C2H3O2)3的水合物中的至少一种。
7.如权利要求1所述的复相巨介电陶瓷材料，其特征在于，所述步骤(2)中的球磨为：以乙醇或丙酮为分散剂，钇稳定的氧化锆球为球磨介质，球磨12小时以上；所述步骤(4)和步骤(5)中，烧结和退火的气氛为空气。
8.如权利要求1所述的复相巨介电陶瓷材料，其特征在于，所述步骤(5)中，表面抛光的工艺为：先用240目的砂纸进行粗抛，后用1200目的砂纸进行细抛。
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