CN106278262A - 一种knn基层状磁电复合材料及其制备方法 - Google Patents

一种knn基层状磁电复合材料及其制备方法 Download PDF

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CN106278262A
CN106278262A CN201610648063.7A CN201610648063A CN106278262A CN 106278262 A CN106278262 A CN 106278262A CN 201610648063 A CN201610648063 A CN 201610648063A CN 106278262 A CN106278262 A CN 106278262A
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knn
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杨海波
张锦涛
林营
朱建锋
王芬
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Shaanxi University of Science and Technology
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Abstract

一种KNN基层状磁电复合材料及其制备方法，分别将(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体、Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体造粒后，按照2‑2复合的垒层叠加排列方式在模具中压制成型，然后排出PVA粘合剂，在1060～1090℃下烧结，即可得到层状磁电复合材料。本发明中两种粉末按照2‑2复合的垒层叠加排列方式，将铁电相和铁磁相以层状复合的方式共烧在一起，可以有效地抑制两相之间的相互反应从而保持各自的特性，使其较高的居里温度、较好的铁电性和铁磁性。

Description

一种KNN基层状磁电复合材料及其制备方法
技术领域
本发明属于材料科学领域，涉及一种高居里温度、高铁电和铁磁性能KNN基层状磁电复合材料及其制备方法。
背景技术
随着移动通讯和计算机技术的飞速发展，使得各种电子设备变得更加高度集成化、多功能化、小型化和快速响应化。由于电子设备的微型化和小型化是必然趋势，因此，迫切需要一种材料同时具有两种或两种以上的性能，以减小电路板有限空间的消耗，进一步实现小型化。基于此，同时具有铁电性和铁磁性的磁电材料应运而生。
磁电复合材料是通过一定的方法将两种单相材料(铁电相和铁磁相)复合而成，同时兼有铁电和铁磁性能。目前，陶瓷基磁电复合材料多选取高压电性能的锆钛酸铅(PZT)与铁氧体进行复合制备而成。近年来，随着环境保护和人类社会可持续发展的需求，研究新型环境友好型无铅磁电复合材料已成为世界发达国家致力研发的热点之一。现阶段，无铅磁电复合材料的铁电相以BaTiO3基为主，但由于在烧结的过程中，Fe3+的扩散到铁电相，导致铁电相的居里温度降低，从而限制磁电复合材料的应用性。而铌酸钾钠(KNN)基压电材料以高居里温度著称，弥补了BaTiO3基压电材料的不足，提高了复合材料的居里温度，从而拓宽了磁电复合材料的适用性。
磁电复合材料分为0-3型磁电复合材料和2-2型磁电复合材料。0-3型磁电复合材料是将不连续的铁电相(铁磁相)颗粒分散于三维连通的铁磁相(铁电相)中，按一定的比例混合，在一定温度下固相烧结，从而得到的颗粒磁电复合材料。此种结构简单，是研究最早、应用最广的一种类型。但由于铁电相(铁磁相)在铁磁(铁电)基体中存在分散不均的问题，因而此种结构类型的材料磁电电压系数较低。
发明内容
本发明的目的在于提供一种高居里温度、优异铁电和铁磁性能的KNN基层状磁电复合材料及其制备方法，将铁电铁磁相以层状复合的方式共烧在一起，可以有效地抑制两相之间的相互反应从而保持各自的特性，使制备的层状磁电复合材料不仅具有较高的居里温度，而且还具有较好的铁电和铁磁性能。
为实现上述目的，本发明采用如下的技术方案：
一种KNN基层状磁电复合材料的制备方法，包括以下步骤：
(1)按照化学式(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且0.1≤x≤0.4，将(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末和Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末按照2-2复合的垒层叠加排列方式在模具中成型，然后采用冷等静压工艺压制；
(2)再于1060～1090℃下烧结2～4小时成瓷，得到层状磁电复合材料。
本发明进一步的改进在于，采用冷等静压工艺在250MPa下压制。
本发明进一步的改进在于，所述步骤(1)中2-2复合的垒层叠加排列方式具体为：从上向下按照(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末、Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末、(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末的顺序垒叠在一起。
本发明进一步的改进在于，(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末通过以下过程制得：按化学式(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3将分析纯的K2CO3、Na2CO3、Li2CO3、Nb2O5、Sb2O5和Ta2O5配制后混合均匀，然后烘干，过筛，压块，再经910～940℃预烧2～5小时，得到块状产品，然后将块状产品粉碎后过120目筛，得到(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体；向(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体中加入PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末。
本发明进一步的改进在于，向(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体中加入PVA粘合剂的质量为(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体质量的8％～15％；混合均匀是通过球磨实现的，球磨的时间为21～24小时。
本发明进一步的改进在于，按化学式式Ni0.37Cu0.20Zn0.43Fe1.92O3.88将分析纯的NiO、CuO、ZnO和Fe2O3配制后混合均匀，然后烘干，过筛，压块，再经790～820℃预烧2～5小时，得到块状固体，然后将块状固体粉碎后过120目筛，得到Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体；向Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体中加入PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末。
本发明进一步的改进在于，向Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体中加入PVA粘合剂的质量为Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体质量的8％～15％；所述PVA粘合剂为质量分数8％的聚乙烯醇水溶液；混合均匀是通过球磨实现的，球磨的时间为5～8小时。
本发明进一步的改进在于，于1060～1090℃下烧结前排除PVA粘合剂，具体是：在温度为550～600℃下保温3～5小时。
一种KNN基层状磁电复合材料，该层状磁电复合材料的化学式为：(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且0.1≤x≤0.4。
与现有技术相比，本发明具有的有益效果：本发明分别将(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体、Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体，按照2-2复合的垒层叠加排列方式在模具中压制成型，在1060～1090℃下烧结，即可得到层状磁电复合材料。本发明中由于(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末、Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末按照2-2复合的垒层叠加排列方式，将铁电相和铁磁相以层状复合的方式共烧在一起，可以有效地抑制两相之间的相互反应从而保持各自的特性，使其既具有较好的铁电性又具有较好的铁磁性。采用共烧的方式，避免了现有技术中直接将两相混合从而产生不可预料的相的问题，进而提高了磁电复合材料的性能，并且该方法仅仅将制得两种粉末压制成型后，烧结，即可得到产品，所以制备方法简单易行。
本发明制得的磁电复合材料具有优异的铁电和磁电性能。复合材料居里温度233～242℃，饱和极化强度Ps为25.1～31.2μC/cm2，饱和磁化强度Ms为6.9～25.7emu/g。
另外，由于本发明采用的原料中不存在铅，所以制备方法不会造成污染，将(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末和Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末按照2-2复合的垒层叠加排列方式烧结在一起，层与层之间不需要粘合剂，因而应力应变的传递可以高效直接的完成。本发明通过将铁电相粉体和铁磁相粉体按照垒层叠加的方式使其共烧在一起，得到电磁复合材料，该电磁复合材料中可较大范围调整压磁相的含量，使磁电电压系数得到大幅度提高。由于电阻率很高的铁电相层可以完全阻断磁性相层的连通，使得材料整体的漏电流较小，有利于材料磁电性能的提高。本发明制得的材料致密性良好，无明显大气孔存在，两相晶粒尺寸均匀，均在亚微米数量级，无明显的界面原子扩散现象，界面耦合较好，所以本发明能够保证磁电复合材料直接高效的磁-电-力转换效率，从而提高了复合材料的磁电转换性能。
附图说明
图1为复合材料(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/Ni0.37Cu0.20Zn0.43Fe1.92O3.88的结构示意图。图中，1为(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末，2为Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末。
图2为1060℃保温2小时烧结所得0.9(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.1Ni0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的介温图谱。
图3为1070℃保温3小时烧结所得0.8(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.2Ni0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的介温图谱。
图4为1080℃保温3.5小时烧结所得0.7(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.3Ni0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的介温图谱。
图5为1090℃保温4小时烧结所得0.6(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.4Ni0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的介温图谱。
图6为1060℃保温2小时烧结所得0.9(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.1Ni0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的电滞回线。
图7为1070℃保温3小时烧结所得(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的电滞回线。
图8为1080℃保温3.5小时烧结所得(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的电滞回线。
图9为1090℃保温4小时烧结所得(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的电滞回线。
图10为1060℃保温2小时烧结所得0.9(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.1Ni0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的磁滞回线。
图11为1070℃保温3小时烧结所得0.8(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.2Ni0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的磁滞回线。
图12为1080℃保温3.5小时烧结所得0.7(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.3Ni0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的磁滞回线。
图13为1090℃保温4小时烧结所得(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的磁滞回线。
图14为1060℃保温2小时烧结所得0.9(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.1Ni0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的界面SEM图。
图15为1070℃保温3小时烧结所得0.8(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.2Ni0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的界面SEM图。
图16为1080℃保温3.5小时烧结所得0.7(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.3Ni0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的界面SEM图。
图17为1090℃保温4小时烧结所得(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88复合材料的界面SEM图。
具体实施方式
下面结合附图及实施例对本发明进行详细说明。本发明中2-2复合的垒层叠加排列方式为：从上向下依次按照铁电相、铁磁相和铁电相的顺序垒叠在一起。
实施例1
层状磁电复合材料的化学式为：(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且x＝0.1。
上述层状磁电复合材料的制备方法，包括以下步骤：
(1)按化学式(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3将分析纯的K2CO3、Na2CO3、Li2CO3、Nb2O5、Sb2O5和Ta2O5配制后通过球磨21小时混合均匀，然后烘干，过筛，压块，再经910℃预烧2小时，得到块状产品，然后将块状产品粉碎后过120目筛，得到(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体；
(2)按化学式式Ni0.37Cu0.20Zn0.43Fe1.92O3.88将分析纯的NiO、CuO、ZnO和Fe2O3配制后通过球磨5小时混合均匀，然后烘干，过筛，压块，再经790℃预烧2小时，得到块状固体，然后将块状固体粉碎后过120目筛，得到Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体；
(3)向(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体中加入(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体质量8％的PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末；向Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体中加入Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体质量8％的PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末；其中，PVA粘合剂为质量分数8％的聚乙烯醇水溶液。
(4)按照化学式(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/
xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且x＝0.1，将(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末和Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末按照2-2复合的垒层叠加排列方式在模具中成型，然后采用冷等静压工艺在250MPa下压制；其中，2-2复合的垒层叠加排列方式具体为：从上向下按照(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末1、Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末2、(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末1的顺序垒叠在一起。
(5)在温度为550℃下保温3小时排除PVA粘合剂后再于1060℃下烧结2小时成瓷，得到KNN基层状磁电复合材料。
图1为复合材料0.9(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.1Ni0.37Cu0.20Zn0.43Fe1.92O3.88的结构示意图。其中，上层为(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末1，中间层为Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末2，下层为(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末1。
由图2可以看出，复合材料具有高的居里温度(233℃)。
由图6可以看出，复合材料具有优异的铁电性能，饱和极化强度为31.2μC/cm2。
由图10可以看出，复合材料具有明显的铁磁性能，饱和磁化强度为6.9emu/g。
由图14可以看出，复合材料致密性良好，无明显大气孔存在，两相晶粒尺寸均匀，均在微米数量级。
实施例2
层状磁电复合材料的化学式为：(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且x＝0.2。
上述层状磁电复合材料的制备方法，包括以下步骤：
(1)按化学式(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3将分析纯的K2CO3、Na2CO3、Li2CO3、Nb2O5、Sb2O5和Ta2O5配制后通过球磨22小时混合均匀，然后烘干，过筛，压块，再经920℃预烧3小时，得到块状产品，然后将块状产品粉碎后过120目筛得到(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体；
(2)按化学式式Ni0.37Cu0.20Zn0.43Fe1.92O3.88将分析纯的NiO、CuO、ZnO和Fe2O3配制后通过球磨6小时混合均匀，然后烘干，过筛，压块，再经800℃预烧3小时，得到块状固体，然后将块状固体粉碎后过120目筛得到Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体；
(3)向(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体中加入(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体质量10％的PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末；向Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体中加入Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体质量10％的PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末；其中，PVA粘合剂为质量分数8％的聚乙烯醇水溶液。
(4)按照化学式(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/
xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且x＝0.2，将(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末和Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末按照2-2复合的垒层叠加排列方式在模具中成型，然后采用冷等静压工艺在250MPa下压制；其中，2-2复合的垒层叠加排列方式具体为：从上向下按照(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末1、Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末2、(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末1的顺序垒叠在一起。
(5)在温度为570℃下保温4小时排除PVA粘合剂后再于1070℃下烧结3小时成瓷，得到KNN基层状磁电复合材料。
图1为复合材料0.9(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.1Ni0.37Cu0.20Zn0.43Fe1.92O3.88的结构示意图。
由图3可以看出，复合材料具有高的居里温度(236℃)。
由图7可以看出，复合材料具有优异的铁电性能，饱和极化强度为30.4μC/cm2。
由图11可以看出，复合材料具有高的铁磁性能，磁电耦合系数为12.6emu/g。
由图15可以看出，复合材料致密性良好，无明显气孔存在，两相晶粒尺寸均匀，均在微米数量级。
实施例3
层状磁电复合材料的化学式为：(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且x＝0.3。
上述层状磁电复合材料的制备方法，包括以下步骤：
(1)按化学式(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3将分析纯的K2CO3、Na2CO3、Li2CO3、Nb2O5、Sb2O5和Ta2O5配制后通过球磨23小时混合均匀，然后烘干，过筛，压块，再经930℃预烧4小时，得到块状产品，然后将块状产品粉碎后过120目筛得到(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体；
(2)按化学式式Ni0.37Cu0.20Zn0.43Fe1.92O3.88将分析纯的NiO、CuO、ZnO和Fe2O3配制后通过球磨7小时混合均匀，然后烘干，过筛，压块，再经810℃预烧4小时，得到块状固体，然后将块状固体粉碎后过120目筛得到Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体；
(3)向(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体中加入(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体质量12％的PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末；向Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体中加入Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体质量12％的PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末；其中，PVA粘合剂为质量分数8％的聚乙烯醇水溶液。
(4)按照化学式(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/
xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且x＝0.3，将(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末和Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末按照2-2复合的垒层叠加排列方式在模具中成型，然后采用冷等静压工艺在250MPa下压制；其中，2-2复合的垒层叠加排列方式具体为：从上向下按照(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末1、Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末2、(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末1的顺序垒叠在一起。
(5)在温度为590℃下保温5小时排除PVA粘合剂后再于1080℃下烧结3.5小时成瓷，得到KNN基层状磁电复合材料。
图1为复合材料0.7(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.3Ni0.37Cu0.20Zn0.43Fe1.92O3.88的结构示意图。
由图4可以看出，复合材料具有较高的居里温度(238℃)。
由图8可以看出，复合材料具有较高的铁电性能，饱和极化强度为28.5μC/cm2。
由图12可以看出，复合材料具有较高的铁磁性能，饱和磁化强度为18.9emu/g。
由图16可以看出，复合材料致密性良好，无明显气孔存在，两相晶粒尺寸均匀，均在微米数量级。
实施例4
层状磁电复合材料的化学式为：(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且x＝0.4。
上述层状磁电复合材料的制备方法，包括以下步骤：
(1)按化学式(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3将分析纯的K2CO3、Na2CO3、Li2CO3、Nb2O5、Sb2O5和Ta2O5配制后通过球磨24小时混合均匀，然后烘干，过筛，压块，再经940℃预烧5小时，得到块状产品，然后将块状产品粉碎后过120目筛得到(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体；
(2)按化学式式Ni0.37Cu0.20Zn0.43Fe1.92O3.88将分析纯的NiO、CuO、ZnO和Fe2O3配制后通过球磨8小时混合均匀，然后烘干，过筛，压块，再经820℃预烧5小时，得到块状固体，然后将块状固体粉碎后过120目筛得到Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体；
(3)向(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体中加入(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体质量15％的PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末；向Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体中加入Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体质量15％的PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末；其中，PVA粘合剂为质量分数8％的聚乙烯醇水溶液。
(4)按照化学式(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/
xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且x＝0.4，将(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末和Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末按照2-2复合的垒层叠加排列方式在模具中成型，然后采用冷等静压工艺在250MPa下压制；其中，2-2复合的垒层叠加排列方式具体为：从上向下按照(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末1、Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末2、(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末1的顺序垒叠在一起。
(5)在温度为600℃下保温6小时排除PVA粘合剂后再于1090℃下烧结4小时成瓷，得到KNN基层状磁电复合材料。
图1为复合材料0.6(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/0.4Ni0.37Cu0.20Zn0.43Fe1.92O3.88的结构示意图。
由图5可以看出，复合材料具有较高的居里温度(242℃)。
由图9可以看出，复合材料具有高的铁电性能，饱和极化强度为25.1μC/cm2。
由图13可以看出，复合材料具有优异的铁磁性能，饱和磁化强度为25.7emu/g。
由图17可以看出，复合材料致密性良好，无明显气孔存在，两相晶粒尺寸均匀，均在微米数量级。
本发明制得的2-2型磁电复合材料，通过将铁电相粉体和铁磁相粉体按照垒层叠加的方式使其共烧在一起的磁电复合材料。此种结构可较大范围调整压磁相的含量，使磁电电压系数得到大幅度提高。由于电阻率很高的铁电相层可以完全阻断磁性相层的连通，使得材料整体的漏电流较小，有利于材料磁电性能的提高。
本发明2-2型(层状)磁电复合材料弥补了0-3型的不足，提高了电阻率，降低了漏电流，从而提高了复合材料的铁电性能和铁磁性能。
(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3是一种压电性材料，具有较高的居里温度和优异的压电性能。Ni0.37Cu0.20Zn0.43Fe1.92O3.88是一种典型的软铁磁材料，具有高的磁导率和低的磁损耗，并具有低温烧结的优点。磁电复合材料(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/Ni0.37Cu0.20Zn0.43Fe1.92O3.88通过叠层累加、冷等静压的方法将铁电相和铁磁相压制成型，低温共烧技术复合而成，同时兼有高居里温度，高的铁电性和铁磁性能。

Claims (9)

1.一种KNN基层状磁电复合材料的制备方法，其特征在于，包括以下步骤：
(1)按照化学式(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且0.1≤x≤0.4，将(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末和Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末按照2-2复合的垒层叠加排列方式在模具中成型，然后采用冷等静压工艺压制；
(2)再于1060～1090℃下烧结2～4小时成瓷，得到层状磁电复合材料。
2.根据权利要求1所述的一种KNN基层状磁电复合材料的制备方法，其特征在于，采用冷等静压工艺在250MPa下压制。
3.根据权利要求1所述的一种KNN基层状磁电复合材料的制备方法，其特征在于，所述步骤(1)中2-2复合的垒层叠加排列方式具体为：从上向下按照(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末、Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末、(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末的顺序垒叠在一起。
4.根据权利要求1所述的一种KNN基层状磁电复合材料的制备方法，其特征在于，(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末通过以下过程制得：按化学式(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3将分析纯的K2CO3、Na2CO3、Li2CO3、Nb2O5、Sb2O5和Ta2O5配制后混合均匀，然后烘干，过筛，压块，再经910～940℃预烧2～5小时，得到块状产品，然后将块状产品粉碎后过120目筛，得到(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体；向(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体中加入PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉末。
5.根据权利要求4所述的一种KNN基层状磁电复合材料的制备方法，其特征在于，向(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体中加入PVA粘合剂的质量为(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3粉体质量的8％～15％；混合均匀是通过球磨实现的，球磨的时间为21～24小时。
6.根据权利要求1所述的一种KNN基层状磁电复合材料的制备方法，其特征在于，按化学式式Ni0.37Cu0.20Zn0.43Fe1.92O3.88将分析纯的NiO、CuO、ZnO和Fe2O3配制后混合均匀，然后烘干，过筛，压块，再经790～820℃预烧2～5小时，得到块状固体，然后将块状固体粉碎后过120目筛，得到Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体；向Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体中加入PVA粘合剂后造粒，再经60目筛网过筛，得到粒径均匀的Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉末。
7.根据权利要求6所述的一种KNN基层状磁电复合材料的制备方法，其特征在于，向Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体中加入PVA粘合剂的质量为Ni0.37Cu0.20Zn0.43Fe1.92O3.88粉体质量的8％～15％；所述PVA粘合剂为质量分数8％的聚乙烯醇水溶液；混合均匀是通过球磨实现的，球磨的时间为5～8小时。
8.根据权利要求6所述的一种KNN基层状磁电复合材料的制备方法，其特征在于，于1060～1090℃下烧结前排除PVA粘合剂，具体是：在温度为550～600℃下保温3～5小时。
9.一种根据权利要求1所述方法制得的KNN基层状磁电复合材料，其特征在于，该层状磁电复合材料的化学式为：(1-x)(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3/xNi0.37Cu0.20Zn0.43Fe1.92O3.88，其中x为Ni0.37Cu0.20Zn0.43Fe1.92O3.88的质量百分数，且0.1≤x≤0.4。
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