CN114804870A - 一种无铅反铁电高储能密度陶瓷材料及其制备方法 - Google Patents

一种无铅反铁电高储能密度陶瓷材料及其制备方法 Download PDF

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CN114804870A
CN114804870A CN202210536338.3A CN202210536338A CN114804870A CN 114804870 A CN114804870 A CN 114804870A CN 202210536338 A CN202210536338 A CN 202210536338A CN 114804870 A CN114804870 A CN 114804870A
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陈骏
祁核
陈良
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Guangzhou Institute For Advanced Material University Of Science & Technology Beijing
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Abstract

本发明提供一种无铅反铁电高储能密度陶瓷材料及其制备方法，所述无铅反铁电高储能密度陶瓷材料的化学通式为(1‑x)(Na0.5Ag0.5)1‑ 3yMyNbO3‑xABO3，其中0＜x≤0.3，0＜y≤0.15；所述ABO3选自BiFeO3、NaTaO3和AgTaO3中的一种；所述的通式中的M选自Bi、La、Ce三价金属的氧化物中的一种或多种，当为多种时，其摩尔分数之和为1；通过结合NaNbO3和AgNbO3这两种无铅反铁电体的优势，构建了(Na0.5Ag0.5)NbO3基体，并且通过高价元素替代A位抑制Ag还原，当向(Na0.5Ag0.5)NbO3中加入其它钙钛矿组成，可以获得稳定的且可逆的反铁电相结构，最终获得高的储能密度，使其能够满足无铅储能电容器中的实际应用需求。

Description

一种无铅反铁电高储能密度陶瓷材料及其制备方法
技术领域
本发明涉及电介质储能陶瓷材料技术领域，具体涉及一种无铅反铁电高储能密度陶瓷材料及其制备方法。
背景技术
当前随着人们日益增长的能源需求，石油等化石燃料不可再生能源被持续不断的消耗，这将使得人类要面临着巨大的能源危机。因此，提高能源利用率和开发新能源已成为世界各国共同关注的问题，同时有些国家把其提升到国家未来生存和发展的重要战略层面。电能的开发和利用已成为缓解当前能源危机的重要途径，寻找电能储存的新材料和新工艺是及其必要的。电介质电容器因具有充放电速度快、寿命时间长等优点，因此，使得它们能满足于不同方面的应用需求。随着科技的发展，在某些方面应用中如脉冲系统等对储能材料提出了新的要求，即具有电容器的优点同时具有高的能量存储密度。通过对电容器及其材料的改性，获得同时具有高能量和功率密度的材料，已成为当前研究的主要方向和热点。目前，用于制备电容器的高储能密度电介质材料的研究主要集中在聚合物、聚合物-陶瓷复合材料以及陶瓷三大类。其中，陶瓷材料具有介电常数高、可调性好、热稳定性好、储能密度高及低的能量损耗等优点，而被广泛应用于储能器件中。
关于储能陶瓷介质材料，其主要可分为线性陶瓷介质、铁电体陶瓷介质和反铁电体陶瓷介质三大类。其中反铁电材料，由于其具有高的饱和极化强度以及低的剩余极化而具有潜力获得高的储能特性，但是大多数的反铁电材料含有对环境以及人体有害的Pb元素，如PbZrO3反铁电材料体系。NaNbO3陶瓷在室温下具有反铁电结构，但纯NaNbO3在施加第一周期电场之后即转变为铁电相。而且除了室温下的反铁电相，其在360℃至480℃之间还存在另外一个反铁电正交相。AgNbO3虽然具有可逆的反铁电特征且具有优异储能性能，但银在烧结过程中易还原且价格昂贵限制了其使用。
发明内容
本发明的目的是针对以上问题，提供一种无铅反铁电高储能密度陶瓷材料及其制备方法，通过结合NaNbO3和AgNbO3这两种无铅反铁电体的优势，构建了(Na0.5Ag0.5)NbO3基体，并且通过高价元素替代A位抑制Ag还原，当向(Na0.5Ag0.5)NbO3中加入其它钙钛矿组成，可以获得稳定的且可逆的反铁电相结构，最终获得高的储能密度，使其能够满足无铅储能电容器中的实际应用需求。
为了实现上述目的，本发明采取的技术方案为：一种无铅反铁电高储能密度陶瓷材料，其化学通式为(1-x)(Na0.5Ag0.5)1-3yMyNbO3-xABO3，其中0＜x≤0.3，0＜y≤0.15；所述ABO3选自BiFeO3、NaTaO3和AgTaO3中的一种；所述的通式中的M选自Bi、La、Ce三价金属的氧化物中的一种或多种，当为多种时，其摩尔分数之和为1。
为解决上述问题，本发明还提供了一种上述无铅反铁电高储能密度陶瓷材料的制备方法，包括如下步骤：
a、将原料按照通式(1-x)(Na0.5Ag0.5)1-3yMyNbO3-xABO3所示化学组成的化学计量比称量化学纯或分析纯的碳酸盐或金属氧化物进行配料；
b、将步骤a配好的原料以酒精或者水为介质，经4-12小时的球磨混料，湿粉经烘干后得到混合粉料；
c、将所述混合粉料放置于氧化铝坩埚中煅烧合成，合成温度为850-1000℃，保温2-4小时，煅烧过程中使用氧气气氛；重复步骤b和c至少一次，完成预煅烧合成预合成粉体；
d、将步骤c得到的预合成粉体经过研碎后仍以酒精或者水为介质球磨6-24小时，干燥后的粉体过100-130目筛后在50-200MPa的压力下制成所需形状的陶瓷坯体；
e、将步骤d得到的陶瓷坯体在空气中常压下采用埋粉末法提供保护气氛烧结，烧结温度为1100-1250℃，烧结时间为1-4小时，升温速率为1-3℃/min，得到陶瓷样品；
f、将步骤e得到的陶瓷样品经过抛光处理后在两端面涂上银电极。
与现有技术相比，本发明具有以下特点以及有益效果：
1、本发明的陶瓷组成同时具有高储能密度和高储能效率，可采用传统压电陶瓷的制备技术和工业用原料获得，具有实用性，其中储能密度大于7J/cm3，储能效率大于78％。
2、本发明的无铅反铁电陶瓷银含量较低，成本较低，且通过A位缺位的方法抑制银还原，工艺重复性好，性能稳定性好。
3、制备的无铅反铁电高储能陶瓷的结构为纯钙钛矿结构，无其他任何杂相，提高了该高储能陶瓷的结构稳定性及可重复使用性。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本发明实施例中0.98(Na0.5Ag0.5)0.7Bi0.1NbO3-0.02NaTaO3陶瓷在不同频率下无铅反铁电高储能密度陶瓷的温度-介电性能；
图2为本发明实施例中0.98(Na0.5Ag0.5)0.7Bi0.1NbO3-0.02NaTaO3陶瓷在室温下的X射线衍射图谱；
图3为本发明实施例中0.98(Na0.5Ag0.5)0.7Bi0.1NbO3-0.02NaTaO3陶瓷的电滞回线。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将接合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。
因此，以下对在附图中提供的本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供一种无铅反铁电高储能密度陶瓷材料，其化学通式为(1-x)(Na0.5Ag0.5)1-3yMyNbO3-xABO3，其中0＜x≤0.3，0＜y≤0.15；所述ABO3选自BiFeO3、NaTaO3和AgTaO3中的一种；所述的通式中的M选自Bi、La、Ce三价金属的氧化物中的一种或多种，当为多种时，其摩尔分数之和为1。通过结合NaNbO3和AgNbO3这两种无铅反铁电体的优势，构建了(Na0.5Ag0.5)NbO3基体，并且通过高价元素替代A位抑制Ag还原，当向(Na0.5Ag0.5)NbO3中加入其它钙钛矿组成，可以获得稳定的且可逆的反铁电相结构，最终获得高的储能密度，使其能够满足无铅储能电容器中的实际应用需求。
本发明还提供了一种上述无铅反铁电高储能密度陶瓷材料的制备方法，包括如下步骤：
a、将原料按照通式(1-x)(Na0.5Ag0.5)1-3yMyNbO3-xABO3所示化学组成的化学计量比称量化学纯或分析纯的碳酸盐或金属氧化物进行配料；
b、将步骤a配好的原料以酒精或者水为介质，经4-12小时的球磨混料，湿粉经烘干后得到混合粉料；
c、将所述混合粉料放置于氧化铝坩埚中煅烧合成，合成温度为850-1000℃，保温2-4小时，煅烧过程中使用氧气气氛；重复步骤b和c至少一次，完成预煅烧合成预合成粉体；
d、将步骤c得到的预合成粉体经过研碎后仍以酒精或者水为介质球磨6-24小时，干燥后的粉体过100-130目筛后在50-200MPa的压力下制成所需形状的陶瓷坯体；本发明中的陶瓷坯体形状为直径10mm、厚度0.5-2mm的圆片；
e、将步骤d得到的陶瓷坯体在空气中常压下采用埋粉末法提供保护气氛烧结，烧结温度为1100-1250℃，烧结时间为1-4小时，升温速率为1-3℃/min，得到陶瓷样品；
f、将步骤e得到的陶瓷样品经过抛光处理后在两端面涂上银电极。涂敷银电极为现有的常规工艺，如将烧结后的陶瓷胚体双面用丝网刷上银浆后，在700-800℃条件下烧渗银电极，得到成品。
通过上述方法所制备的高储能密度陶瓷为纯钙钛矿结构，可以使得本发明的陶瓷组成同时具有高储能密度和高储能效率，可采用传统压电陶瓷的制备技术和工业用原料获得，具有实用性，其中储能密度大于7J/cm3，储能效率大于78％；其次，本发明的无铅反铁电陶瓷银含量较低，成本较低，且通过A位缺位的方法抑制银还原，工艺重复性好，性能稳定性好；制备的无铅反铁电高储能陶瓷的结构为纯钙钛矿结构，无其他任何杂相，提高了该高储能陶瓷的结构稳定性及可重复使用性。
实施例1
本实施例提供的无铅反铁电高储能密度陶瓷材料的制备方法，包括如下步骤：
a、将分析纯的Na2CO3、Nb2O5、Ag2O、Bi2O3、Ta2O5，按按化学式0.98(Na0.5Ag0.5)0.7Bi0.1NbO3-0.02NaTaO3中的化学计量比称取上述各原料后混合，得混合物；
b、将上述配好的原料以酒精为介质，经6小时的球磨混料；湿粉经烘干后得到混合粉料；
c、将得到的混合粉料放置于氧化铝坩埚中煅烧合成，合成温度为850℃，氧气气氛保温4小时；重复步骤b和c一次，完成预煅烧合成；
d、将得到的预合成粉体经过研碎后仍以酒精为介质球磨12小时，干燥后的粉体过100目筛后在100MPa的压力下冷压成型直径10mm、厚度1mm的圆片，得到陶瓷坯体；
e、将得到的陶瓷坯体在空气中常压下采用埋粉末法提供保护气氛烧结，并置于倒放的双坩埚中，即将陶瓷坯体和粉末放置于双坩埚叠置所形成的空间内，烧结温度为1200℃，烧结时间为2小时、升温速率为3℃/min，得到陶瓷样品；
f、将得到的陶瓷样品经过抛光处理后在两端面涂上银电极。
由此得到0.98(Na0.5Ag0.5)0.7Bi0.1NbO3-0.02NaTaO3的无铅陶瓷。图1为不同频率下无铅反铁电高储能密度陶瓷的温度-介电性能；采用X-射线衍射分析仪(XRD)来确定预烧粉体和陶瓷样品的晶体结构和相结构；采用铁电分析仪测试陶瓷及玻璃陶瓷样品的电滞回线。高压测试时，将样品放在硅油中，防止表面放电。性能如下：在150℃以内，其相对介电常数为620，且不同频率下介电常数相差不大；该成分样品的XRD图谱显示为纯钙钛矿结构；通过电滞回线算得储能性能为7.5J/cm3，储能效率80％。
实施例2
本实施例提供的无铅反铁电高储能密度陶瓷材料的制备方法，包括如下步骤：
a、将分析纯的Na2CO3、Nb2O5、Ag2O、La2O3、Bi2O3、Ta2O5、Fe2O3按按化学式0.9(Na0.5Ag0.5)0.97La0.01NbO3-0.1BiFeO3中的化学计量比称取上述各原料后混合，得混合物；
b、将上述配好的原料以酒精为介质，经6小时的球磨混料；湿粉经烘干后得到混合粉料；
c、将得到的混合粉料放置于氧化铝坩埚中煅烧合成，合成温度为900℃，氧气气氛保温4小时；重复步骤b和c两次，完成预煅烧合成；
d、将得到的预合成粉体经过研碎后仍以酒精为介质球磨24小时，干燥后的粉体过100目筛后在100MPa的压力下冷压成型直径10mm、厚度1mm的圆片，得到陶瓷坯体；
e、将得到的陶瓷坯体在空气中常压下采用埋粉末法提供保护气氛烧结，并置于倒放的双坩埚中，即将陶瓷坯体和粉末放置于双坩埚叠置所形成的空间内，烧结温度为1200-1250℃，烧结时间为2小时、升温速率为3℃/min，得到陶瓷样品；
f、将得到的陶瓷样品经过抛光处理后在两端面涂上银电极。
由此得到0.9(Na0.5Ag0.5)0.97La0.01NbO3-0.1BiFeO3的无铅陶瓷。测试方法如实施例1，性能如下：在150℃以内，其相对介电常数为650，且不同频率下介电常数相差不大；该成分样品的XRD图谱显示为纯钙钛矿结构；通过电滞回线算得储能性能为7.9J/cm3，储能效率82％。
实施例3
本实施例提供的无铅反铁电高储能密度陶瓷材料的制备方法，包括如下步骤：
a、将分析纯的Na2CO3、Nb2O5、Ag2O、La2O3、Ta2O5按按化学式0.95(Na0.5Ag0.5)0.7La0.1NbO3-0.05NaTaO3中的化学计量比称取上述各原料后混合，得混合物；
b、将上述配好的原料以酒精为介质，经6小时的球磨混料；湿粉经烘干后得到混合粉料；
c、将得到的混合粉料放置于氧化铝坩埚中煅烧合成，合成温度为900℃，氧气气氛保温4小时；重复步骤b和c两次，完成预煅烧合成；
d、将得到的预合成粉体经过研碎后仍以酒精为介质球磨24小时，干燥后的粉体过100目筛后在100MPa的压力下冷压成型直径10mm、厚度1mm的圆片，得到陶瓷坯体；
e、将得到的陶瓷坯体在空气中常压下采用埋粉末法提供保护气氛烧结，并置于倒放的双坩埚中，即将陶瓷坯体和粉末放置于双坩埚叠置所形成的空间内，烧结温度为1230℃，烧结时间为2小时、升温速率为3℃/min，得到陶瓷样品；
f、将得到的陶瓷样品经过抛光处理后在两端面涂上银电极。
由此得到0.95(Na0.5Ag0.5)0.7La0.1NbO3-0.05NaTaO3的无铅陶瓷。测试方法如实施例1，性能如下：在150℃以内，其相对介电常数为630，且不同频率下介电常数相差不大；该成分样品的XRD图谱显示为纯钙钛矿结构；通过电滞回线算得储能性能为7.9J/cm3，储能效率84％。
实施例4
本实施例提供的无铅反铁电高储能密度陶瓷材料的制备方法，包括如下步骤：
a、将分析纯的Na2CO3、Nb2O5、Ag2O、Ce2O3、Ta2O5按按化学式0.85(Na0.5Ag0.5)0.7Ce0.1NbO3-0.15NaTaO3中的化学计量比称取上述各原料后混合，得混合物；
b、将上述配好的原料以酒精为介质，经4.5小时的球磨混料；湿粉经烘干后得到混合粉料；
c、将得到的混合粉料放置于氧化铝坩埚中煅烧合成，合成温度为950℃，氧气气氛保温3小时；重复步骤b和c两次，完成预煅烧合成；
d、将得到的预合成粉体经过研碎后仍以酒精为介质球磨6-7小时，干燥后的粉体过120目筛后在55MPa的压力下冷压成型直径10mm、厚度1.5mm的圆片，得到陶瓷坯体；
e、将得到的陶瓷坯体在空气中常压下采用埋粉末法提供保护气氛烧结，并置于倒放的双坩埚中，即将陶瓷坯体和粉末放置于双坩埚叠置所形成的空间内，烧结温度为1100℃，烧结时间为4小时、升温速率为2℃/min，得到陶瓷样品；
f、将得到的陶瓷样品经过抛光处理后在两端面涂上银电极。
由此得到0.85(Na0.5Ag0.5)0.7Ce0.1NbO3-0.15NaTaO3的无铅陶瓷。测试方法如实施例1，性能如下：在150℃以内，其相对介电常数为680，且不同频率下介电常数相差不大；该成分样品的XRD图谱显示为纯钙钛矿结构；通过电滞回线算得储能性能为8.5J/cm3，储能效率83％。
实施例5
本实施例提供的无铅反铁电高储能密度陶瓷材料的制备方法，包括如下步骤：
a、将分析纯的Na2CO3、Nb2O5、Ag2O、La2O3、Ta2O5按按化学式0.7(Na0.5Ag0.5)0.97La0.01NbO3-0.3AgTaO3中的化学计量比称取上述各原料后混合，得混合物；
b、将上述配好的原料以酒精为介质，经8小时的球磨混料；湿粉经烘干后得到混合粉料；
c、将得到的混合粉料放置于氧化铝坩埚中煅烧合成，合成温度为1000℃，氧气气氛保温2小时；重复步骤b和c两次，完成预煅烧合成；
d、将得到的预合成粉体经过研碎后仍以酒精为介质球磨12小时，干燥后的粉体过130目筛后在200MPa的压力下冷压成型直径10mm、厚度1mm的圆片，得到陶瓷坯体；
e、将得到的陶瓷坯体在空气中常压下采用埋粉末法提供保护气氛烧结，并置于倒放的双坩埚中，即将陶瓷坯体和粉末放置于双坩埚叠置所形成的空间内，烧结温度为1250℃，烧结时间为1小时、升温速率为3℃/min，得到陶瓷样品；
f、将得到的陶瓷样品经过抛光处理后在两端面涂上银电极。
由此得到0.7(Na0.5Ag0.5)0.97La0.01NbO3-0.3AgTaO3的无铅陶瓷。测试方法如实施例1，性能如下：在150℃以内，其相对介电常数为700，且不同频率下介电常数相差不大；该成分样品的XRD图谱显示为纯钙钛矿结构；通过电滞回线算得储能性能为8.8J/cm3，储能效率84％。
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (2)

1.一种无铅反铁电高储能密度陶瓷材料，其特征在于，
其化学通式为(1-x)(Na0.5Ag0.5)1-3yMyNbO3-xABO3，其中0＜x≤0.3，0＜y≤0.15；
所述ABO3选自BiFeO3、NaTaO3和AgTaO3中的一种；
所述的通式中的M选自Bi、La、Ce三价金属的氧化物中的一种或多种，当为多种时，其摩尔分数之和为1。
2.一种根据权利要求1所述的无铅反铁电高储能密度陶瓷材料的制备方法，其特征在于，包括如下步骤：
a、将原料按照通式(1-x)(Na0.5Ag0.5)1-3yMyNbO3-xABO3所示化学组成的化学计量比称量化学纯或分析纯的碳酸盐或金属氧化物进行配料；
b、将步骤a配好的原料以酒精或者水为介质，经4-12小时的球磨混料，湿粉经烘干后得到混合粉料；
c、将所述混合粉料放置于氧化铝坩埚中煅烧合成，合成温度为850-1000℃，保温2-4小时，煅烧过程中使用氧气气氛；重复步骤b和c至少一次，完成预煅烧合成预合成粉体；
d、将步骤c得到的预合成粉体经过研碎后仍以酒精或者水为介质球磨6-24小时，干燥后的粉体过100-130目筛后在50-200MPa的压力下制成所需形状的陶瓷坯体；
e、将步骤d得到的陶瓷坯体在空气中常压下采用埋粉末法提供保护气氛烧结，烧结温度为1100-1250℃，烧结时间为1-4小时，升温速率为1-3℃/min，得到陶瓷样品；
f、将步骤e得到的陶瓷样品经过抛光处理后在两端面涂上银电极。
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