CN113563073B - 一种高稳定的无铅压电陶瓷及其制备方法 - Google Patents
一种高稳定的无铅压电陶瓷及其制备方法 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 230000010287 polarization Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229920002994 synthetic fiber Polymers 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 abstract description 2
- 239000010432 diamond Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 description 10
- 238000010168 coupling process Methods 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 10
- 238000006467 substitution reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017676 MgTiO3 Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- ACNRWWUEFJNUDD-UHFFFAOYSA-N lead(2+);distiborate Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-][Sb]([O-])([O-])=O.[O-][Sb]([O-])([O-])=O ACNRWWUEFJNUDD-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明涉及一种高稳定的无铅压电陶瓷，所述无铅压电陶瓷的化学式如下：(1‑x‑y)(0.50KNbO3‑0.50NaNbO3)‑xMgTiO3‑yBa(Zr0.5Ti0.5)O3+zSm2O3；其中，x＝0.03～0.07，y＝0.04～0.08，z＝0.008～0.02。该无铅压电陶瓷采用一种工艺简单、高效率、低能耗、成本低廉且很具实用性的无铅压电陶瓷的制备方法，制得的KNN‑MT‑BZT无铅压电陶瓷烧后的晶粒为菱形，而且晶粒平均晶粒为3微米，取代之前的KNN体系的烧后的四方形晶粒，密度更高，性质稳定、致密、性能良好。
Description
技术领域
本发明涉及钙钛矿结构无铅压电陶瓷技术领域，尤其是涉及一种高稳定的无铅压电陶瓷及其制备方法。
背景技术
压电陶瓷及压电陶瓷器件已广泛地应用于工业特别是信息产业领域。以锆钛酸铅（Pb(Ti，Zr)O3）为代表的铅基二元系和以锆钛酸铅（Pb(Ti，Zr)O3）为基、添加第三组元如以铌镁酸铅(Pb(Mg1/3Nb2/3)O3）、锑锰酸铅Pb(Mn1/3Sb2/3)O3为代表的铅基三元系压电陶瓷具有优良的压电铁电性能、高的居里温度。工业生产中应用的压电陶瓷绝大多数是该类钙钛矿铅基压电陶瓷。
但是，铅基压电陶瓷中，PbO或Pb3O4的含量约占原料总质量的65%。铅污染已成为人类公害之一。铅基压电陶瓷在生产、使用及废弃后处理过程中给人类及生态环境造成严重危害，不利于人类社会的可持续发展。近年来，开发不含铅的、性能优越的压电陶瓷体系受到世界各国特别是欧美、日本、韩国以及中国的日益重视。
目前广泛研究的无铅压电陶瓷体系有四类：铋层状结构无铅压电陶瓷、BaTiO3基无铅压电陶瓷、Bi0.5Na0.5TiO3基无铅压电陶瓷及K0.5Na0.5NbO3碱金属铌酸盐系无铅压电陶瓷。其中KNN系无铅压电陶瓷因具有介电常数小、压电性能高、频率常数大、密度小、居里温度高等特点，成为当前最有可能取代铅基压电陶瓷的体系之一。然而，传统工艺获得KNN压电陶瓷有以下的缺点：(1)在1140℃以上，KNN会出现液相，所以KNN的温度稳定性被限制在1140℃以下。(2)由于在900℃左右Na和K会以氧化物Na2O和K2O形成开始挥发，造成预烧和烧结的气氛很难控制；(3)KNN在潮湿的环境时非常容易发生潮解，使化学计量发生偏离，导致产生杂相，使陶瓷难以烧结致密。上述原因都限制了KNN体系材料的实际应用。
为了优化KNN基无铅压电陶瓷的结构，提高KNN基陶瓷的压电性能，各国学者从添加烧结助剂、A位和B位掺杂取代、添加新组元等方面对KNN基无铅压电陶瓷进行了大量研究；同时，结合热压、放电等离子、热等静压烧结等工艺方法，以期获得致密的KNN陶瓷；然而上述制备方法对设备要求过高、生产工艺苛刻、生产成本较高、材料尺寸受到限制，而且制得的陶瓷的稳定性也不能令人满意，因此难以获得工业化应用。
发明内容
为了克服现有技术存在的上述技术问题，本发明的第一目的在于提供一种高稳定的无铅压电陶瓷，所述无铅压电陶瓷的化学式如下：(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3；其中，x=0.03~0.07，y=0.04~0.08，z=0.008~0.02。
优选的，所述无铅压电陶瓷的化学式如下：(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3；其中，x=0.05，y=0.06，z=0.015。在合成反应温度为850℃，烧成温度为1230℃下制备的该无铅压电陶瓷，其综合压电性能最好，其中，εr为2300、tanδ为0.013、kp为46.8％、d33为392pC/N，较高的居里温度Tc为315℃，其密度ρ=4.339g/cm3。
本发明的第二目的在于提供一种上述的高稳定的无铅压电陶瓷的制备方法，其包括如下步骤：
S01配料：首先按照上述的高稳定的无铅压电陶瓷的成分计算并称取原料Na2CO3、K2CO3、Nb2O5、TiO2，MgO，BaCO3，ZrO2和Sm2O3，然后将所述原料于球磨罐中球磨混合，得到混合的粉体；
S02合成：将步骤S01得到的混合的粉体烘干后，于氧化铝坩埚内、密封条件下、800℃～950℃合成反应2.5h，得到合成的物料；
S03成型及排塑：首先将步骤S02得到的合成的物料球磨混合、烘干后流延成膜、冲制成坯体，然后将所述坯体的经两段升温至400℃，保温60min后，以5℃/min的速率将所述坯体升温至650℃保温120min，以便排出有机物；其中，物料：流延水剂的重量比=100:1。所述坯体的直径为17.20mm，厚度为12.5±0.5um。所述两段升温为：先以3℃/min的速率将坯体升温至200℃，再以2℃/min速率将坯体从200℃升温至400℃。
S04烧结：将步骤S03得到的排出有机物后的坯体用步骤S02所得的部分物料埋烧：以3℃/min速率升温至1230℃，保温2小时，随炉冷却，得到烧结的坯体；
S05被覆银电极、烧银：将步骤S04得到的烧结的坯体超声水洗烘干后被银，再置于加热炉中，升温至800℃保温10min后自然冷却至室温，得到烧银制品；其中，所述被银采用丝网印刷工艺。
S06极化：将步骤S05得到的烧银制品，于100℃的空气中，施加1500V/mm的直流电场，极化10min，得到高稳定的无铅压电陶瓷。
进一步的，步骤S01和S03中球磨混合的条件为：球磨介质为去离子水和ZrO2球，球磨罐的转速为750r/min，球磨时间为2.5h。且原料/物料：ZrO2球：去离子水的重量比=1：2.5：1。
进一步的，步骤S02、S03和S05中的烘干均是在60～100℃干燥箱中烘干。
相对现有技术，本发明的有益效果在于：
（1）传统的KNN体系在1140度时，氧化物Na2O和K2O会挥发很多，导致产品的密度及性能偏低，无法大批商业应用。本发明是加入xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3 这些物质，防止在1230度高温烧结的Na2O和K2O的挥发，形成致密的陶瓷体，并提高产品的密度及电性能。
（2）现有技术可以用热压、放电等离子、热等静压烧结等工艺方法，是可以获得高致密的KNN陶瓷，但烧结设备昂贵，需要加入保护气氛、高精密的模具，成本比本方法的通常的空气烧结1230度，不用加压的方式高出多倍（至少5倍）。
（3）本发明无铅压电陶瓷，相对于纯的KNN无铅压电陶瓷，表现出显著的压电和铁电性能、较高的居里温度及最佳的压电热稳定性等优点，其压电性能都得到了显著的改善，能够用于压电表贴蜂鸣器及压电陶瓷驱动器等电子器件，能够满足上述电子器件对无铅压电陶瓷的压电性能的较高要求，其具有光明的市场前景和开发潜力。
本发明无铅压电陶瓷的制备方法是一种工艺简单、高效率、低能耗、成本低廉且很具实用性的无铅压电陶瓷制备方法，制得的KNN-MT-BZT无铅压电陶瓷烧后的晶粒为菱形，而且晶粒平均晶粒为3微米，取代之前的KNN体系的烧后的四方形晶粒，密度更高不易吸潮，性质稳定、致密、性能良好。
附图说明
图1为介电常数εT 33/ε0的变化图，其中，X轴为(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3中MgTiO3的取代量X，Y轴为介电常数εT 33/ε0值。
图2为压电系数d33的变化图谱，其中，X轴为(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3中yBa(Zr0.5Ti0.5)O3的取代量Y，Y轴为压电系数d33，单位为pC/N。
图3为机电耦合系数KP的变化图谱，其中，X轴为(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3中Sm2O3的取代量Z，Y轴为机电耦合系数KP，为百分数。
图4为(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3的产品烧后晶粒。
具体实施方式
下面结合具体实施例对本发明做进一步的分析，显然，所描述的仅仅是本发明一部分实施例，而不是全部的实施例。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的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。
实施例和对比例
本发明的实施例和对比例中，所用的原料均为市售产品，其中Na2CO3、K2CO3、Nb2O5、TiO2，MgO，BaCO3，ZrO2及Sm2O3均为化学纯。本发明具体实施例和对比例提供的压电陶瓷按照下述方法制备，不同的是（BaXMgYWZ）的取代量和合成反应温度。
一种高稳定的无铅压电陶瓷的制备方法，其包括如下步骤：
S01配料：首先按照高稳定的无铅压电陶瓷的化学式【(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3；其中，x=0.03~0.07，y=0.04~0.08，z=0.008~0.02】的成分计算并称取原料Na2CO3、K2CO3、Nb2O5、TiO2，MgO，BaCO3，ZrO2和Sm2O3，然后将所述原料于球磨罐中球磨混合，得到混合的粉体；其中，球磨介质为去离子水和ZrO2球，原料：ZrO2球：去离子水的重量比=1：2.5：1，球磨罐的转速为750r/min，球磨时间为2.5h。
S02合成：将步骤S01得到的混合的粉体在60～100℃干燥箱中烘干，然后放入氧化铝坩埚内、加盖密封、于800℃～950℃合成反应2.5h，得到合成的(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3物料；
S03成型及排塑：首先将步骤S02得到的合成的(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3物料球磨混合（其中，球磨介质为去离子水和ZrO2球，物料：ZrO2球：去离子水的重量比=1：2.5：1，球磨罐的转速为750r/min，球磨时间为2.5h）、在60～100℃干燥箱中烘干，按照(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3物料：流延水剂的重量比=100:1，向烘干后的(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3物料加入现有的流延水剂，搅拌均匀后在自动流延机里流延成厚度为1-50um的膜片，冲制成直径为17.20mm，厚度为12.5±0.5um的坯体；然后将所述坯体先以3℃/min的速率将坯体升温至200℃，再以2℃/min速率将坯体从200℃升温至400℃，在400℃保温60min后，以5℃/min的速率将所述坯体升温至650℃保温120min，以便排出有机物。
S04烧结：将步骤S03得到的排出有机物后的坯体在密闭容器中用步骤S02所得的部分(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3物料埋烧：以避免坯体烧结过程中KNa的挥发导致产品中组分的变化。烧结条件为：以3℃/min速率升温至1230℃，保温2小时，随炉冷却，得到烧结的坯体；
S05被覆银电极、烧银：将步骤S04得到的烧结的坯体在常温下、20-100khz的频率下超声水洗30min，然后在60～100℃干燥箱中烘干后采用丝网印刷工艺被银，再置于加热炉中，升温至800℃保温10min后自然冷却至室温，得到烧银制品。
S06极化：将步骤S05得到的烧银制品，于极化箱中100℃的空气中，施加1500V/mm的直流电场，极化10min，得到高稳定的无铅压电陶瓷。
测试方法
本发明实施例和对比例提供的压电陶瓷，于室温下放置24小时后，测试其压电性能参数损耗值tanδ、介电常数εT 33/ε0、压电系数d33和机电耦合系数KP、密度，具体测试方法如下：
1．损耗值tanδ和介电常数εT 33/ε0的测试方法：可以使用中国天津市无线电六厂生产的4225型LCR自动测量仪，在室温下测量压电陶瓷试样的损耗值tanδ，测试频率为1Kz；在上述相同的条件下，测试电容，由下式计算介电常数εT 33/ε0：
式中，
C—电容，F，
t—压电陶瓷试样的厚度，cm，
Φ—压电陶瓷试样的圆形银电极直径，cm，
ε0—真空介电常数，F/m。
2．压电系数d33的测试方法：可以依据国标GB11309-89规定的方法，采用中科院声学所提供的ZJ-3A型准静态测试仪，测试压电系数d33，其单位为pC/N。
3．机电耦合系数KP的测试方法：采用谐振-反谐振法测量计算得到机电耦合系数KP，具体方法是由HP4294A精密阻抗分析仪测量压电振子谐振频率fr与反谐振频率fa，根据以下公式计算机电耦合系数KP：
式中：
fr--谐振频率，
fa--反谐振频率。
4．样品的密度通过测量直径、厚度和质量求得每个组分计算三个样品求平均。采用高级衍射测量系统获取陶瓷射线衍射数据。
对本发明实施例和对比例提供的压电陶瓷，采用上述方法测试其压电性能，其损耗值tanδ、介电常数εT 33/ε0、压电系数d33和机电耦合系数KP值、密度具体见表2所示。
结合表1和表2可看出：当X = 0.05，Y= 0.06， Z = 0.015，合成反应温度为850℃时，烧成温度为1230℃，所获得的改性的压电陶瓷综合压电性能最好，其中，εr为2300、tanδ为0.013、Kp为46.8％、d33为392pC/N，其密度ρ=4.339 g/cm3，且经测试其较高的居里温度Tc为315℃。
从图1可以看出，与纯的KNN压电陶瓷相比，MgTiO3复合取代改性的压电陶瓷的介电常数εT 33/ε0得到了提高。在不同合成温度下，(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3中Ba的取代量X的增加，介电常数εT 33/ε0呈现递增的趋势，当取代量X=0.05时，介电常数εT 33/ε0达到最大值，且当合成温度为850℃时，介电常数εT 33/ε0达到最大值为1600。
从图2可以看出，yBa(Zr0.5Ti0.5)O3复合取代改性的压电陶瓷的压电系数d33得到了提高。
从图3可以看出，Sm2O3加入改性的压电陶瓷的机电耦合系数KP得到了提高。随着(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3中Sm2O3的取代量Z的增加，机电耦合系数KP呈现递增的趋势，当取代量X=0.015时，机电耦合系数KP达到最大值，随着其加入量的增加，KP又下降。
从图4可以看出，(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3无铅压电陶瓷烧后的晶粒为菱形，而且晶粒平均晶粒为3微米，取代之前的KNN体系的烧后的四方形晶粒。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本发明的保护范围。
Claims (9)
1.一种高稳定的无铅压电陶瓷，其特征在于，所述无铅压电陶瓷烧后的晶粒为菱形，平均晶粒为3微米，且所述无铅压电陶瓷的化学式如下：
(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3；其中，x=0.03~0.07，y=0.04~0.08，z=0.008~0.02；
所述的高稳定的无铅压电陶瓷的通过如下方法制备所得，其具体包括如下步骤：
S01配料：首先按照上述的高稳定的无铅压电陶瓷的成分计算并称取原料Na2CO3、K2CO3、Nb2O5、TiO2，MgO，BaCO3，ZrO2和Sm2O3，然后将所述原料于球磨罐中球磨混合，得到混合的粉体；
S02合成：将步骤S01得到的混合的粉体烘干后，于氧化铝坩埚内、密封条件下、800℃～950℃合成反应2.5h，得到合成的物料；
S03成型及排塑：首先将步骤S02得到的合成的物料球磨混合、烘干后流延成膜、冲制成坯体，然后将所述坯体的经两段升温至400℃，保温60min后，以5℃/min的速率将所述坯体升温至650℃保温120min，以便排出有机物；
S04烧结：将步骤S03得到的排出有机物后的坯体用步骤S02所得的部分物料埋烧：以3℃/min速率升温至1230℃，保温2小时，随炉冷却，得到烧结的坯体；
S05被覆银电极、烧银：将步骤S04得到的烧结的坯体超声水洗烘干后被银，再置于加热炉中，升温至800℃保温10min后自然冷却至室温，得到烧银的制品；
S06极化：将步骤S05得到的烧银制品，于100℃的空气中，施加1500V/mm的直流电场，极化10min，得到高稳定的无铅压电陶瓷。
2.根据权利要求1所述的高稳定的无铅压电陶瓷，其特征在于，所述无铅压电陶瓷的化学式如下：
(1-x-y)(0.50KNbO3-0.50NaNbO3)-xMgTiO3-yBa(Zr0.5Ti0.5)O3+zSm2O3；其中，x=0.05，y=0.06，z=0.015。
3.根据权利要求1所述的高稳定的无铅压电陶瓷，其特征在于，步骤S01和S03中球磨混合的条件为：球磨介质为去离子水和ZrO2球，球磨罐的转速为750r/min，球磨时间为2.5h。
4.根据权利要求1所述的高稳定的无铅压电陶瓷，其特征在于，原料/物料：ZrO2球：去离子水的重量比=1：2.5：1。
5.根据权利要求1所述的高稳定的无铅压电陶瓷，其特征在于，步骤S02、S03和S05中的烘干均是在60～100℃干燥箱中烘干。
6.根据权利要求1所述的高稳定的无铅压电陶瓷，其特征在于，步骤S03中物料：流延水剂的重量比=100:1。
7.根据权利要求1所述的高稳定的无铅压电陶瓷，其特征在于，步骤S03中所述坯体的直径为17.20mm，厚度为12.5±0.5um。
8.根据权利要求1所述的高稳定的无铅压电陶瓷，其特征在于，步骤S03中所述两段升温为：先以3℃/min的速率将坯体升温至200℃，再以2℃/min速率将坯体从200℃升温至400℃。
9.根据权利要求1所述的高稳定的无铅压电陶瓷，其特征在于，步骤S05所述被银是采用丝网印刷工艺。
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