CN112321293A - 一种高磁导率高频高阻抗高居里温度锰锌铁氧体材料及其制备方法 - Google Patents

一种高磁导率高频高阻抗高居里温度锰锌铁氧体材料及其制备方法 Download PDF

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CN112321293A
CN112321293A CN202011207677.4A CN202011207677A CN112321293A CN 112321293 A CN112321293 A CN 112321293A CN 202011207677 A CN202011207677 A CN 202011207677A CN 112321293 A CN112321293 A CN 112321293A
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manganese
temperature
ferrite material
curie temperature
impedance
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朱勇
王朝明
赵旭
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Hengdian Group DMEGC Magnetics Co Ltd
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Hengdian Group DMEGC Magnetics Co Ltd
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Priority to CN202011207677.4A priority Critical patent/CN112321293A/zh
Publication of CN112321293A publication Critical patent/CN112321293A/zh
Priority to DE112021005797.9T priority patent/DE112021005797T5/de
Priority to PCT/CN2021/116619 priority patent/WO2022095577A1/zh
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Abstract

本发明属于软磁铁氧体材料技术领域，公开了一种高磁导率高频高阻抗高居里温度锰锌铁氧体材料及其制备方法。本发明的高磁导率高频高阻抗高居里温度锰锌铁氧体材料由主成份和辅助成分组成，所述主成份由以下摩尔百分比的原料组成：52～54mol％的Fe2O3，18～22mol％的ZnO，其余为MnO；以主成份总量为基准，所述辅助成分由以下含量的原料组成：CaCO3200～1000ppm，Bi2O3200～1000ppm，Co2O3200～1000ppm，MoO3200～1000ppm。采用本发明的配方及工艺制得的锰锌铁氧体材料具有高磁导率高频高阻抗高居里温度特性：初始磁率μi(25℃)≥12000，Tc≥150℃，0.5‑1.0MHz的范围内，阻抗系数≥26Ω/mm。

Description

一种高磁导率高频高阻抗高居里温度锰锌铁氧体材料及其制 备方法
技术领域
本发明涉及软磁铁氧体材料技术领域，具体是涉及一种高磁导率高频高阻抗高居里温度锰锌铁氧体材料及其制备方法。
背景技术
随着移动通信、卫星通信、计算机等电子技术领域的高速发展和普遍应用，我们周围形成了一种我们无法感知的无形的污染——电子产品辐射与泄露造成的电磁干扰(EMI)。EMI不仅对电子设备本身产生干扰，从而影响电子设备的正常工作，而且还会对人类的健康产生一定的威胁，为此，人们利用抗电磁波干扰材料来消除电磁波辐射与泄露造成的电磁干扰。
作为抗电磁干扰材料，要求衰减速度快，频带范围宽，同时应保证工作频率范围的信号不失真，能适应各种环境使用。因此，作为抗EMI用的软磁铁氧体材料一般应具有以下特点：(1)高磁导率；(2)具有较高的居里温度；(3)高频高阻抗；(4)良好的温度稳定性。
目前应用最广泛，最具有经济性的抗EMI用的软磁铁氧体材料为锰锌铁氧体材料。市场上现有的抗EMI锰锌铁氧体材料已经达到了高磁导率和高频高阻抗的特性，但是这些抗EMI锰锌铁氧体材料都存在着居里温度低和温度稳定性差等问题。例如，Ferroxcube公司的3E12虽然磁导率达到12000，但居里温度为130℃；横店东磁公司的R12K磁导率为12000，居里温度也在130℃附近。又如中国专利文献CN111056830A公开了一种宽温高频高阻抗高磁导率锰锌铁氧体材料，该发明以Fe2O3、Mn3O4、ZnO作为铁氧体主成分，同时添加TiO2、NiO、MoO3、SiO2和Bi2O3作为辅助成分使得室温下的起始磁导率可以达到12000以上，但是居里温度只有137℃。再如中国专利文献CN106747396A公开了一种汽车电子用高磁导率锰锌铁氧体材料及其制备方法，该发明的铁氧体材料由主料和掺杂剂组成，其主料包括：52～53mol％Fe2O3，17～20.5mol％ZnO，其余为MnO，添加剂为分析纯级的CuO、CaCO3、Ta2O5、In2O3、Bi2O3，该发明的铁氧体材料的居里温度达到150℃，磁导率只有10000左右，并且在二峰位置和一峰位置之间存在磁导率低于10000的情况。因此，制备一种高磁导率高频高阻抗高居里温度锰锌铁氧体材料是有必要的。
发明内容
本发明的目的是为了克服上述背景技术的不足，提供一种高磁导率高频高阻抗高居里温度锰锌铁氧体材料及其制备方法，所述高磁导率高频高阻抗高居里温度是指所述锰锌铁氧体材料有以下几个特点：(1)起始磁导率μi≥12000；(2)居里温度Tc≥150℃；(3)200KHz条件下，起始磁导率μi≥10000；(4)0.5-1MHz条件下，阻抗系数≥26Ω/mm。此外，本发明制备的锰锌铁氧体材料在25-80℃范围内温度稳定性好。
为达到本发明的目的，本发明的高磁导率高频高阻抗高居里温度锰锌铁氧体材料由主成份和辅助成分组成，所述主成份由以下摩尔百分比的原料组成：52～54mol％的Fe2O3，18～22mol％的ZnO，其余为MnO；以主成份总量为基准，所述辅助成分由以下含量的原料组成：CaCO3 200～1000ppm，Bi2O3 200～1000ppm，Co2O3 200～1000ppm，MoO3 200～1000ppm。
优选地，在本发明的一些实施例中，所述主成份由以下摩尔百分比的原料组成：52.40mol％的Fe2O3，27.20mol％的MnO，20.40mol％的ZnO；按占主成分总量计，所述辅助成分组成为CaCO3 200ppm，Bi2O3 500ppm，Co2O3 200ppm，MoO3 200ppm。
进一步地，本发明还提供了一种前述高磁导率高频高阻抗高居里温度锰锌铁氧体材料的制备方法，所述方法包括以下步骤：
(1)一次球磨混料：按配比分别称取主成分各原料，通过球磨混匀得浆料，对浆料进行喷雾干燥得到粉料；
(2)预烧：将粉料进行预烧，得预烧料；
(3)二次球磨：按配比称取辅助成分添加至预烧料中，加去离子水进行二次球磨得浆料；
(4)喷雾造粒：在二次球磨所得浆料中加入胶水PVA混匀后进行喷雾造粒得颗粒料；
(5)成型：对喷雾造粒后的颗粒料进行压制成型得锰锌铁氧体毛坯；
(6)烧结：将成型后的锰锌铁氧体毛坯放入烧结设备中进行烧结。
进一步地，所述步骤(1)中一次球磨时间为30-40min。
进一步地，所述步骤(2)中预烧温度为700-900℃，预烧时间为170-190min。
进一步地，所述步骤(3)中二次球磨时间为60-90min。
优选地，所述二次球磨料的粒度分布控制在X50：1.2-1.4μm；X99：6.0-8.0μm。
Xb＝aμm表示粒径小于aμm的粒径占总体积的b％。上述X50为中位径，是平均粒径的一种表示形式，表示二次砂磨料中小于1.2-1.4μm的颗粒占50％；X99表示二次砂磨料中小于6.0-8.0μm的颗粒占99％。
进一步地，所述步骤(4)中喷雾造粒所得颗粒料的粒径为50-200μm。
进一步地，所述步骤(5)中锰锌铁氧体毛坯密度控制为3.05-3.1g/cm3。
进一步地，所述步骤(6)中烧结包括以下阶段：
(a)一次升温及保温：用8-10h将温度从室温升温至800-1000℃，保温至材料质量不再减少为止，该阶段烧结气氛为空气；
(b)二次升温及保温：用7-9h将温度继续升温至1350-1450℃，在最高温度下保温6-8h，烧结气氛中氧分压控制范围为3-7vol％，其余气氛为不与材料发生反应的保护气氛；
(c)降温：用8-10h将温度降低至1100℃，气氛保持为不同温度的平衡氧分压，在降温过程中，烧结气氛中氧分压控制在0.12-5vol％，其余气氛为不与材料发生反应的保护气氛，且随着温度的降低，氧分压降低；
(d)最终降温：以2.5-3.5℃/min的速率冷却至室温，得高磁导率高频高阻抗高居里温度锰锌铁氧体材料，此阶段烧结气氛中氧分压低于0.12vol％。
作为优选，阶段(c)中，所述不同温度的平衡氧分压按照以下公式的计算：lgPO2＝a-b/T，其中，PO2为氧分压的大小，a取3～8，b为常数，取14000～15000，T为热力学温度。
本发明特别针对烧结工艺做了分阶段烧结气氛及升温速率、氧分压的控制，必须严格按照上述参数的设计去完成烧结，才能够制得高磁导率高频高阻抗高居里温度锰锌铁氧体材料。
与现有技术相比，本发明的优点如下：
(1)本发明的MnZn铁氧体材料配方中，设计ZnO的摩尔比多于20mol％的高锌配方，可以大大提高磁导率，又通过Fe2O3、Co2O3和其他几种添加剂的协同增效，相互作用，使其晶粒尺寸增大且生长均匀，使各向异性常数K1趋近于0，不仅可提高其磁导率，又可以改善材料的温度稳定性，提高材料的居里温度；
(2)本发明制备工艺严格控制加料顺序及工艺参数，采用本发明的烧结方式，可以大规模量产磁芯样品，实现低成本的生产方式，从而实现大规模、低成本、批量化生产高磁导率高频高阻抗高居里温度锰锌铁氧体材料；
(3)采用本发明的配方及工艺制得的锰锌铁氧体材料具有高磁导率高频高阻抗高居里温度特性：初始磁率μi(25℃)≥12000，Tc≥150℃，0.5-1.0MHz的范围内，阻抗系数≥26Ω/mm。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。应当理解，以下描述仅仅用以解释本发明，并不用于限定本发明。
本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1至5”时，所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。
此外，下面所描述的术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不是必须针对相同的实施例或示例。而且，在本发明中，若非特指，所有设备和原料均可从市场购得或是本行业常用的，下述实施例中的方法，如无特别说明，均为本领域常规方法，本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
将配比为Fe2O3 52.80mol％、MnO 26.90mol％、ZnO 20.30mol％(换算成质量百分比为Fe2O3：69.48wt％、Mn3O4：16.91wt％、ZnO：13.62wt％)的三种主原料进行一次球磨混合，然后在850℃下进行预烧，在预烧料中添加辅助成分CaCO3 200ppm、Bi2O3 400ppm、Co2O3500ppm、MoO3 200ppm，混合后通过二次球磨、烘干、造粒、压制成型，最后在推板窑中进行烧结，烧结工艺为：以2℃/min的升温速率加热至1000℃，该阶段烧结气氛为空气，然后以0.8℃/min的升温速率加热至1410℃，保温6h，氧分压浓度控制在5vol％，降温至1100℃后氧分压浓度控制在0.03vol％以下，最后以3℃/min的速率降温至室温。
采用10匝绕线，在3302仪器上测得电压在0.25v，频率在10KHz条件下的磁导率温度特性，在3302仪器上测得电压在0.25v的磁导率频率特性和阻抗频率特性，测试结果见表1-3。
实施例2
将配比为Fe2O3 52.00mol％、MnO 27.60mol％、ZnO 20.40mol％(换算成质量百分比为Fe2O3：68.80wt％、Mn3O4：17.44wt％、ZnO：13.76wt％)的三种主原料进行一次球磨混合，然后在850℃下进行预烧，在预烧料中添加辅助成分CaCO3 200ppm、Bi2O3 400ppm、Co2O3500ppm、MoO3 200ppm，混合后通过二次球磨、烘干、造粒、压制成型，最后在推板窑中进行烧结，烧结工艺为：以2℃/min的升温速率加热至1000℃，该阶段烧结气氛为空气，然后以0.8℃/min的升温速率加热至1410℃，保温6h，氧分压浓度控制在5vol％，降温至1100℃后氧分压浓度控制在0.03vol％以下，最后以3℃/min的速率降温至室温。
采用10匝绕线，在3302仪器上测得电压在0.25v，频率在10KHz条件下的磁导率温度特性，在3302仪器上测得电压在0.25v的磁导率频率特性和阻抗频率特性，测试结果见表1-3。
实施例3
采用与实施例2同样配方的毛坯在推板窑中进行排胶烧结，烧结工艺为：以2℃/min的升温速率加热至1000℃，该阶段烧结气氛为空气，然后以1.5℃/min的升温速率加热至1360℃，保温6h，氧分压浓度控制在5vol％，降温至1100℃后氧分压浓度控制在0.03vol％以下，最后以3℃/min的速率降温至室温。
采用10匝绕线，在3302仪器上测得电压在0.25v，频率在10KHz条件下的磁导率温度特性，在3302仪器上测得电压在0.25v的磁导率频率特性和阻抗频率特性，测试结果见表1-3。
实施例4
将配比为Fe2O3 52.40mol％、MnO 27.20mol％、ZnO 20.40mol％(换算成质量百分比为Fe2O3：69.14wt％、Mn3O4：17.14wt％、ZnO：13.72wt％)的三种主原料进行一次球磨混合，然后在850℃下进行预烧，在预烧料中添加辅助成分CaCO3 200ppm、Bi2O3 400ppm、Co2O3500ppm、MoO3 200ppm，混合后通过二次球磨、烘干、造粒、压制成型，最后进行烧结，烧结工艺为：以2℃/min的升温速率加热至1000℃，该阶段烧结气氛为空气，然后以0.8℃/min的升温速率加热至1410℃，保温6h，氧分压浓度控制在5vol％，降温至1100℃处氧分压浓度控制在0.03vol％以下，最后以3℃/min的速率降温至室温。
采用10匝绕线，在3302仪器上测得电压在0.25v，频率在10KHz条件下的磁导率温度特性，在3302仪器上测得电压在0.25v的磁导率频率特性和阻抗频率特性，测试结果见表1-3。
实施例5
采用与实施例4同样配方的毛坯在推板窑中进行排胶烧结，烧结工艺为：以2℃/min的升温速率加热至1000℃，该阶段烧结气氛为空气，然后以0.8℃/min的升温速率加热至1410℃，保温6h，氧分压浓度控制在3vol％，降温至1100℃后氧分压浓度控制在0.03vol％以下，最后以3℃/min的速率降温至室温。
采用10匝绕线，在3302仪器上测得电压在0.25v，频率在10KHz条件下的磁导率温度特性，在3302仪器上测得电压在0.25v的磁导率频率特性和阻抗频率特性，测试结果见表1-3。
实施例6
采用与实施例4同样配方的毛坯在推板窑中进行排胶烧结，烧结工艺为：以2℃/min的升温速率加热至1000℃，该阶段烧结气氛为空气，然后以0.8℃/min的升温速率加热至1410℃，保温6h，氧分压浓度控制在7vol％，降温至1100℃后氧分压浓度控制在0.03vol％以下，最后以3℃/min的速率降温至室温。
采用10匝绕线，在3302仪器上测得电压在0.25v，频率在10KHz条件下的磁导率温度特性，在3302仪器上测得电压在0.25v的磁导率频率特性和阻抗频率特性，测试结果见表1-3。
实施例7
采用实施例4的主成分配方作为目标进行中试，总量由小试的400g扩大到400kg，同样采用实施例4的辅助成分配方，经过一次球磨、喷雾干燥、预烧、砂磨、喷雾造粒、压制成型，最终推板窑中进行排胶烧结。其中在二次砂磨后需要对浆料成分进行补正，从而使其达到目标成分：Fe2O3 52.40mol％、MnO 27.20mol％、ZnO 20.40mol％(换算成质量百分比为Fe2O3：69.14wt％、Mn3O4：17.14wt％、ZnO：13.72wt％)。烧结工艺为：以2℃/min的升温速率加热至1000℃，该阶段烧结气氛为空气，然后以0.8℃/min的升温速率加热至1410℃，保温6h，氧分压浓度控制在5vol％，降温至1100℃后氧分压浓度控制在0.03vol％以下，最后以3℃/min的速率降温至室温。
采用10匝绕线，在3302仪器上测得电压在0.25v，频率在10KHz条件下的磁导率温度特性，在3302仪器上测得电压在0.25v的磁导率频率特性和阻抗频率特性，测试结果见表1-3。
对比例1
在实施例4的基础上，保证主配方为Fe2O3 52.40mol％、MnO 27.20mol％、ZnO20.40mol％(换算成质量百分比为Fe2O3：69.14wt％、Mn3O4：17.14wt％、ZnO：13.72wt％)的三种主原料进行一次球磨混合，然后在850℃下进行预烧，在预烧料中添加辅助成分CaCO3200ppm、Bi2O3 500ppm、Co2O3 200ppm、MoO3200ppm，其余工艺与实施例4相同。
采用10匝绕线，在3302仪器上测得电压在0.25v，频率在10KHz条件下的磁导率温度特性，在3302仪器上测得电压在0.25v的磁导率频率特性和阻抗频率特性，测试结果见表1-3。
结果显示：室温下10KHz起始磁导率μi达到了12000以上，居里温度也达到了150℃，磁导率的比温度系数aμ/μ1(*10-6)为0.0305，表明磁导率随温度变化很小，并且磁导率在200KHZ的条件下还能保持在10000以上。
对比例2
在实施例4的基础上，降低Fe2O3的含量，增加ZnO的含量，主配方为Fe2O352.30mol％、MnO 27.00mol％、ZnO 20.70mol％(换算成质量百分比为Fe2O3：69.04wt％、Mn3O4：17.04wt％、ZnO：13.92wt％)然后在850℃下进行预烧，在预烧料中添加辅助成分CaCO3 200ppm、Bi2O3 500ppm、Co2O3 750ppm、MoO3 200ppm，其余工艺与实施例4相同。
采用10匝绕线，在3302仪器上测得电压在0.25v，频率在10KHz条件下的磁导率温度特性，在3302仪器上测得电压在0.25v的磁导率频率特性和阻抗频率特性，测试结果见表1-3。
结果显示：室温下10KHz起始磁导率μi虽然达到了13000以上，但是居里温度不能达到150℃。
对比例3
采用对比例1的配方作为目标进行中试，总量由小试的400g扩大到400kg，同样采用对比例1的辅助成分配方，经过一次球磨、喷雾干燥、预烧、砂磨、喷雾造粒、压制成型，最终推板窑中进行排胶烧结。其中在二次砂磨后需要对浆料成分进行补正，从而使其达到目标成分：Fe2O3 52.40mol％、MnO 27.20mol％、ZnO 20.40mol％(换算成质量百分比为Fe2O3：69.14wt％、Mn3O4：17.14wt％、ZnO：13.72wt％)。烧结工艺为：以2℃/min的升温速率加热至1000℃，该阶段烧结气氛为空气，然后以0.8℃/min的升温速率加热至1410℃，保温6h，氧分压浓度控制在5vol％，降温至1100℃后氧分压浓度控制在0.03vol％以下，最后以3℃/min的速率降温至室温。
采用10匝绕线，在3302仪器上测得电压在0.25v，频率在10KHz条件下的磁导率温度特性，在3302仪器上测得电压在0.25v的磁导率频率特性和阻抗频率特性，测试结果见表1-3。
结果显示：中试投料完全能够达到小试对比例1的磁性能，表明可以按照对比例3的配方和工艺进行量产。
对比例4
采用对比例3中试后的颗粒料进行压环烧结，放到钟罩炉中烧结，烧结工艺为：以0.7℃/min的升温速率加热至950℃排胶，该阶段烧结气氛为空气，然后以2℃/min的升温速率加热至1370(该阶段烧结气氛为氮气)保温5.5h(该阶段烧结气氛中氧分压为21vol％)，接着再保温1h(该阶段烧结气氛中氧分压为5vol％)，降温至1200℃处氧分压设为2vol％，保温1h,最终以3℃/min的速率降至室温。
采用10匝绕线，在3302仪器上测得电压在0.25v，频率在10KHz条件下的磁导率温度特性，在3302仪器上测得电压在0.25v的磁导率频率特性和阻抗频率特性，测试结果见表1-3。
结果显示：钟罩炉烧结可以改善阻抗的频率特性，但是钟罩炉烧结的效率比推板窑炉低，并且生产成本也比推板窑高。
性能测试结果
表1不同温度磁导率对比表
Figure BDA0002757582950000111
表2不同频率磁导率对比表
频率(KHZ) 10 100 200 300
实施例1 7607 7051 7121 5960
实施例2 7742 7542 7335 6005
实施例3 6097 5864 5782 4958
实施例4 11474 11436 10036 6899
实施例5 9978 9566 8769 6200
实施例6 10625 10442 9046 6270
实施例7 11265 11226 9763 6835
对比例1 12019 12226 10117 6977
对比例2 13194 13097 10669 7334
对比例3 11913 12252 10195 7047
对比例4 12028 12142 9967 6838
表3不同频率阻抗(Ω/mm)对比表
频率(KHZ) 300 500 800 1000
实施例1 ≥14 ≥17 ≥16 ≥15
实施例2 ≥15 ≥20 ≥21 ≥21
实施例3 ≥15 ≥20 ≥21 ≥21
实施例4 ≥20 ≥24 ≥24 ≥23
实施例5 ≥18 ≥21 ≥20 ≥20
实施例6 ≥19 ≥23 ≥22 ≥22
实施例7 ≥21 ≥24 ≥24 ≥23
对比例1 ≥24 ≥28 ≥27 ≥26
对比例2 ≥23 ≥28 ≥27 ≥26
对比例3 ≥24 ≥28 ≥27 ≥26
对比例4 ≥24 ≥30 ≥31 ≥30
本领域的技术人员容易理解，以上所述仅为本发明的实施例而已(所述对比例的技术方案只要落入发明内容内也是本申请拟保护的技术方案，之所以表述为对比例是为了对比说明)，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种高磁导率高频高阻抗高居里温度锰锌铁氧体材料，其特征在于，所述高磁导率高频高阻抗高居里温度锰锌铁氧体材料由主成份和辅助成分组成，所述主成份由以下摩尔百分比的原料组成：52～54mol％的Fe2O3，18～22mol％的ZnO，其余为MnO；以主成份总量为基准，所述辅助成分由以下含量的原料组成：CaCO3 200～1000ppm，Bi2O3 200～1000ppm，Co2O3 200～1000ppm，MoO3 200～1000ppm。
2.根据权利要求1所述的高磁导率高频高阻抗高居里温度锰锌铁氧体材料，其特征在于，所述主成份由以下摩尔百分比的原料组成：52.40mol％的Fe2O3，27.20mol％的MnO，20.40mol％的ZnO；按占主成分总量计，所述辅助成分组成为CaCO3 200ppm，Bi2O3 500ppm，Co2O3 200ppm，MoO3 200ppm。
3.根据权利要求1所述的高磁导率高频高阻抗高居里温度锰锌铁氧体材料，其特征在于，所述高磁导率高频高阻抗高居里温度是指所述锰锌铁氧体材料有以下特点：(1)起始磁导率μi≥12000；(2)居里温度Tc≥150℃；(3)200KHz条件下，起始磁导率μi≥10000；(4)0.5-1MHz条件下，阻抗系数≥26Ω/mm。
4.权利要求1-3任一项所述高磁导率高频高阻抗高居里温度锰锌铁氧体材料的制备方法，其特征在于，所述方法包括以下步骤：
(1)一次球磨混料：按配比分别称取主成分各原料，通过球磨混匀得浆料，对浆料进行喷雾干燥得到粉料；
(2)预烧：将粉料进行预烧，得预烧料；
(3)二次球磨：按配比称取辅助成分添加至预烧料中，加去离子水进行二次球磨得浆料；
(4)喷雾造粒：在二次球磨所得浆料中加入胶水PVA混匀后进行喷雾造粒得颗粒料；
(5)成型：对喷雾造粒后的颗粒料进行压制成型得锰锌铁氧体毛坯；
(6)烧结：将成型后的锰锌铁氧体毛坯放入烧结设备中进行烧结。
5.根据权利要求4所述高磁导率高频高阻抗高居里温度锰锌铁氧体材料的制备方法，其特征在于，所述步骤(1)中一次球磨时间为30-40min。
6.根据权利要求4所述高磁导率高频高阻抗高居里温度锰锌铁氧体材料的制备方法，其特征在于，所述步骤(2)中预烧温度为700-900℃，预烧时间为170-190min。
7.根据权利要求4所述高磁导率高频高阻抗高居里温度锰锌铁氧体材料的制备方法，其特征在于，所述步骤(3)中二次球磨时间为60-90min；优选地，所述二次球磨料的粒度分布控制在X50：1.2-1.4μm；X99：6.0-8.0μm。
8.根据权利要求4所述高磁导率高频高阻抗高居里温度锰锌铁氧体材料的制备方法，其特征在于，所述步骤(4)中喷雾造粒所得颗粒料的粒径为50-200μm。
9.根据权利要求4所述高磁导率高频高阻抗高居里温度锰锌铁氧体材料的制备方法，其特征在于，所述步骤(5)中锰锌铁氧体毛坯密度控制为3.05-3.1g/cm3。
10.根据权利要求4所述高磁导率高频高阻抗高居里温度锰锌铁氧体材料的制备方法，其特征在于，所述步骤(6)中烧结包括以下阶段：
(a)一次升温及保温：用8-10h将温度从室温升温至800-1000℃，保温至材料质量不再减少为止，该阶段烧结气氛为空气；
(b)二次升温及保温：用7-9h将温度继续升温至1350-1450℃，在最高温度下保温6-8h，烧结气氛中氧分压控制范围为3-7vol％，其余气氛为不与材料发生反应的保护气氛；
(c)降温：用8-10h将温度降低至1100℃，气氛保持为不同温度的平衡氧分压，在降温过程中，烧结气氛中氧分压控制在0.12-5vol％，其余气氛为不与材料发生反应的保护气氛，且随着温度的降低，氧分压降低；
(d)最终降温：以2.5-3.5℃/min的速率冷却至室温，得高磁导率高频高阻抗高居里温度锰锌铁氧体材料，此阶段烧结气氛中氧分压低于0.12vol％；
作为优选，阶段(c)中，所述不同温度的平衡氧分压按照以下公式的计算：lgPO2＝a-b/T，其中，PO2为氧分压的大小，a取3～8，b为常数，取14000～15000，T为热力学温度。
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