CN114566382A - Ceramic dielectric material and preparation method and application thereof - Google Patents
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- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- 239000003989 dielectric material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 40
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 21
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
- 239000002019 doping agent Substances 0.000 claims abstract description 4
- 230000015556 catabolic process Effects 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 6
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims description 6
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 6
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims 4
- 229910052681 coesite Inorganic materials 0.000 claims 3
- 229910052906 cristobalite Inorganic materials 0.000 claims 3
- 239000000377 silicon dioxide Substances 0.000 claims 3
- 229910052682 stishovite Inorganic materials 0.000 claims 3
- 229910052905 tridymite Inorganic materials 0.000 claims 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005245 sintering Methods 0.000 abstract description 13
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- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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Abstract
本发明提供一种陶瓷介质材料及其制备方法及应用，所述材料的主体材料为BaTiO3，掺杂材料包括SiO2、CaO、V2O5、ZrO2和稀土元素的氧化物；所述稀土元素的氧化物包括Sc2O3、Sm2O3、Dy2O3、Ho2O3中的至少两种；按摩尔百分比计，BaTiO3的添加量为93.5～95mol％；掺杂材料的总添加量为4.6～7mol％。本发明以BaTiO3作为主体材料，以烧结助剂、金属氧化物及稀土元素作为复合掺杂剂，对钛酸钡陶瓷基体进行改性，并添加烧结助剂以及掺杂材料细化颗粒，控制缺陷及提升晶粒尺寸均匀性，制备出具有高可靠性，稳定电容特性且更易叠层的细晶陶瓷与多层陶瓷电容器。The invention provides a ceramic dielectric material, a preparation method and application thereof. The main material of the material is BaTiO 3 , and the doping material includes SiO 2 , CaO, V 2 O 5 , ZrO 2 and oxides of rare earth elements; Oxides of rare earth elements include at least two of Sc 2 O 3 , Sm 2 O 3 , Dy 2 O 3 , and Ho 2 O 3 ; in terms of mol percentage, the addition amount of BaTiO 3 is 93.5-95 mol %; doping material The total addition amount is 4.6 to 7 mol%. In the present invention, BaTiO3 is used as the main material, sintering aids, metal oxides and rare earth elements are used as composite dopants to modify the barium titanate ceramic matrix, and sintering aids and doping materials are added to refine the particles to control Defects and improved grain size uniformity, to prepare fine-grained ceramics and multilayer ceramic capacitors with high reliability, stable capacitance characteristics and easier lamination.
Description
技术领域technical field
本发明涉及陶瓷介质材料，具体涉及一种陶瓷介质材料及其制备方法和应用。The invention relates to a ceramic dielectric material, in particular to a ceramic dielectric material and a preparation method and application thereof.
背景技术Background technique
多层陶瓷电容器(MLCC)利用独石结构实现了多个电容并联增大容量的效果，因其成本低、高容量、较稳定等特点广泛用于通讯设备、汽车电子、产业机器、医疗机器等领域的通信基础设备电路中。例如，其可作为电源旁路电容器，如液晶模块(液晶驱动电压线路)、高电源电压的LSI/IC/OP放大器，或作为平滑电容器，如DC-DC变换器(输入和输出)、开关电源(二次侧)等。近年来，移动电子设备的小型化使得MLCC逐渐向小型化、大容量的方向发展。其中，钛酸钡(BaTiO3)是MLCC中Ⅱ类电容器的基体材料，其具有较高的介电常数，但想要得到大容量的钛酸钡基MLCC，需增加叠层数量，而叠层数量便会导致MLCC的可靠性大幅下降。除此之外，Ⅱ类电容器的介电材料容温系数有X5R、X6R、X7R等，由美国电子工业协会(EIA)电容器规范中提到，X5R对应于温度-55℃～85℃之间时，相对于25℃的电容量变化率在+15％到-15％之间。而钛酸钡的介电常数在-90℃、0℃和125℃时波动很大，如此特性也限制了钛酸钡的应用范围。Multilayer Ceramic Capacitors (MLCC) utilize the monolithic structure to achieve the effect of increasing the capacity of multiple capacitors in parallel. Because of their low cost, high capacity, and stability, they are widely used in communication equipment, automotive electronics, industrial machines, medical machines, etc. field of communication infrastructure circuits. For example, it can be used as a power supply bypass capacitor, such as liquid crystal modules (liquid crystal driving voltage lines), LSI/IC/OP amplifiers with high power supply voltage, or as smoothing capacitors, such as DC-DC converters (input and output), switching power supplies (Secondary side) etc. In recent years, the miniaturization of mobile electronic devices makes MLCCs gradually develop in the direction of miniaturization and large capacity. Among them, barium titanate (BaTiO 3 ) is the base material of type II capacitors in MLCCs, which has a high dielectric constant, but to obtain large-capacity barium titanate-based MLCCs, it is necessary to increase the number of stacks, and the stacks The number will lead to a significant decrease in the reliability of MLCCs. In addition, the temperature coefficients of dielectric materials for Class II capacitors include X5R, X6R, X7R, etc., as mentioned in the American Electronics Industry Association (EIA) capacitor specification, X5R corresponds to the temperature between -55 ℃ ~ 85 ℃ , the capacitance change rate relative to 25°C is between +15% and -15%. The dielectric constant of barium titanate fluctuates greatly at -90°C, 0°C and 125°C, which also limits the application range of barium titanate.
为了克服上述问题，急需对钛酸钡材料其进行改性掺杂、稀土掺杂、制备出超纯超细且分散性良好的粉体，以达到细化晶粒，提高晶粒尺寸和分布的均匀性，从而显著改善MLCC产品的耐压特性和可靠性。In order to overcome the above problems, it is urgent to modify the barium titanate material, doping it with rare earth, and prepare ultra-pure, ultra-fine and well-dispersed powders, so as to refine the grains and improve the grain size and distribution. uniformity, thereby significantly improving the withstand voltage characteristics and reliability of MLCC products.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术存在的不足之处而提供一种陶瓷介质材料及其制备方法和应用。本发明主要选择烧结助剂、金属氧化物及稀土元素作为复合掺杂剂，对钛酸钡陶瓷基体进行改性，并添加烧结助剂以及掺杂材料细化颗粒，控制缺陷及提升晶粒尺寸均匀性，制备具有高可靠性，稳定电容特性且更易叠层的细晶陶瓷与多层陶瓷电容器。The purpose of the present invention is to overcome the deficiencies of the prior art and provide a ceramic dielectric material and its preparation method and application. The present invention mainly selects sintering aids, metal oxides and rare earth elements as composite dopants, modifies the barium titanate ceramic matrix, and adds sintering aids and doping materials to refine particles to control defects and increase grain size Uniformity, preparation of fine-grained ceramic and multilayer ceramic capacitors with high reliability, stable capacitance characteristics and easier lamination.
为实现上述目的，本发明采取的技术方案为：To achieve the above object, the technical scheme adopted in the present invention is:
一种陶瓷介质材料，所述材料的主体材料为BaTiO3，掺杂材料包括SiO2、CaO、V2O5、ZrO2和稀土元素的氧化物；所述稀土元素的氧化物包括Sc2O3、Sm2O3、Dy2O3、Ho2O3中的至少两种；按摩尔百分比计，BaTiO3的添加量为93.5～95mol％；掺杂材料的总添加量为4.6～7mol％。A ceramic dielectric material, the main material of the material is BaTiO 3 , the doping material includes SiO 2 , CaO, V 2 O 5 , ZrO 2 and oxides of rare earth elements; the oxides of rare earth elements include Sc 2 O 3. At least two kinds of Sm 2 O 3 , Dy 2 O 3 and Ho 2 O 3 ; in terms of mole percentage, the addition amount of BaTiO 3 is 93.5-95 mol %; the total addition amount of the doping material is 4.6-7 mol % .
本发明以BaTiO3作为主体材料，通过优化掺杂材料的类型、配方及比重，制备具有高击穿强度、高可靠性的共掺杂钛酸钡陶瓷介电材料。其中，添加SiO2作为烧结助剂，降低和加宽烧结温度，防止陶瓷颗粒在烧结过程中的晶粒长大；添加CaO和少量Sc2O3以细化晶粒，并共同促进BaTiO3的传质过程提高陶瓷致密度；而SiO2与CaO的组合会在陶瓷烧结过程中产生液相，液相均匀包裹每个颗粒，防止颗粒过度长大，除此之外，内电极表面的液相可以阻碍金属元素向介质层扩散，增强MLCC的可靠性，增加了本发明在MLCC应用领域的优异性；为防止Ti4+离子在还原气氛下烧结时还原成Ti3+产生氧空位，加入V2O5让可以发生变价的V元素取代钛酸钡(BT)中的Ti位，从而抑制氧空位的产生，提高剩余极化强度和高温可靠性；适量ZrO2的加入也可以提高Ti离子的带隙和还原焓，从而降低氧空位的浓度。另外，本发明创造性地选择稀土氧化物Dy2O3与少量Sm2O3或Ho2O3混合作为共掺杂材料，在陶瓷晶粒中形成“芯-壳”结构，弥补了单一稀土元素离子迁移率固定使得壳层元素浓度不均的缺点，有助于实现掺杂元素浓度由晶粒壳部向芯部的均匀梯度，避免均一性差导致的复杂缺陷形态以提高可靠性，并借此稳定温度对电容的影响。 The invention uses BaTiO3 as the main material, and prepares the co-doped barium titanate ceramic dielectric material with high breakdown strength and high reliability by optimizing the type, formula and specific gravity of the doping material. Among them, SiO 2 was added as a sintering aid to reduce and widen the sintering temperature to prevent the grain growth of ceramic particles during the sintering process; CaO and a small amount of Sc 2 O 3 were added to refine the grains and jointly promote the sintering of BaTiO 3 The mass transfer process improves the density of the ceramic; while the combination of SiO 2 and CaO will generate a liquid phase during the ceramic sintering process, and the liquid phase evenly wraps each particle to prevent excessive particle growth. In addition, the liquid phase on the inner electrode surface It can hinder the diffusion of metal elements to the dielectric layer, enhance the reliability of MLCC, and increase the superiority of the present invention in the application field of MLCC; in order to prevent Ti 4+ ions from being reduced to Ti 3+ during sintering in a reducing atmosphere to generate oxygen vacancies, adding V 2 O 5 replaces the Ti site in barium titanate (BT) with the V element that can change its valence, thereby inhibiting the generation of oxygen vacancies, improving the remanent polarization and high temperature reliability; the addition of an appropriate amount of ZrO 2 can also improve the Ti ions. band gap and reduction enthalpy, thereby reducing the concentration of oxygen vacancies. In addition, the present invention creatively selects the rare earth oxide Dy 2 O 3 mixed with a small amount of Sm 2 O 3 or Ho 2 O 3 as the co-doping material to form a "core-shell" structure in the ceramic grains, making up for a single rare earth element The defect of uneven concentration of shell elements due to the fixed ion mobility helps to achieve a uniform gradient of doping element concentration from the shell to the core of the grain, avoiding complex defect morphology caused by poor uniformity and improving reliability. The effect of stable temperature on capacitance.
作为本发明的优选实施方式，所述掺杂材料包括SiO2 1.2-1.5mol％，CaO 1.6-2.0mol％，Sc2O3 0.4-0.6mol％，V2O5 0.6-0.9mol％，ZrO2 0.3-0.5mol％，Sm2O3 0-0.4mol％，Dy2O3 0.5-0.7mol％，Ho2O3 0-0.4mol％。As a preferred embodiment of the present invention, the doping material includes SiO 2 1.2-1.5 mol %, CaO 1.6-2.0 mol %, Sc 2 O 3 0.4-0.6 mol %, V 2 O 5 0.6-0.9 mol %, ZrO 2 0.3-0.5mol%, Sm2O3 0-0.4mol %, Dy2O3 0.5-0.7mol %, Ho2O3 0-0.4mol %.
作为本发明的优选实施方式，所述稀土元素的氧化物包括Dy2O3、Sc2O3以及Sm2O3、Ho2O3中的至少一种。As a preferred embodiment of the present invention, the oxides of rare earth elements include at least one of Dy 2 O 3 , Sc 2 O 3 , Sm 2 O 3 and Ho 2 O 3 .
作为本发明的优选实施方式，所述掺杂材料包括SiO2 1.2-1.4mol％，CaO 1.6-2.0mol％，Sc2O3 0.4-0.6mol％，V2O5 0.6-0.9mol％，ZrO2 0.3-0.5mol％，Sm2O3 0.3-0.4mol％，Dy2O3 0.5-0.7mol％，Ho2O3 0.3～0.4mol％。As a preferred embodiment of the present invention, the doping material includes SiO 2 1.2-1.4 mol %, CaO 1.6-2.0 mol %, Sc 2 O 3 0.4-0.6 mol %, V 2 O 5 0.6-0.9 mol %, ZrO 2 0.3-0.5mol%, Sm2O3 0.3-0.4mol %, Dy2O3 0.5-0.7mol %, Ho2O3 0.3-0.4mol % .
作为本发明的优选实施方式，所述主体材料BaTiO3的晶粒尺寸为180-240nm。As a preferred embodiment of the present invention, the grain size of the host material BaTiO 3 is 180-240 nm.
发明人经过研究发现，采用常用的固相法BaTiO3粉体材料，能够降低工艺复杂程度，节约成本。BaTiO3纳米颗粒烧结制成多层陶瓷电容器(MLCC)后晶粒尺寸长大20％-35％，故控制主体BaTiO3粉体的颗粒尺寸在180-240nm，以得到最终陶瓷晶粒在200-320nm。The inventor found through research that the use of the commonly used solid-phase method BaTiO 3 powder material can reduce the complexity of the process and save the cost. After BaTiO3 nanoparticles are sintered into multilayer ceramic capacitors (MLCC), the grain size grows by 20 %-35%, so the particle size of the main BaTiO3 powder is controlled to be 180-240nm to obtain the final ceramic grain size of 200- 320nm.
本发明还提供上述陶瓷介质材料的制备方法，将主体材料BaTiO3和掺杂材料按照配方量进行湿法球磨，干燥后即可得到陶瓷介电材料。The present invention also provides a method for preparing the above ceramic dielectric material. The main material BaTiO 3 and the doping material are subjected to wet ball milling according to the formula amount, and the ceramic dielectric material can be obtained after drying.
作为本发明的优选实施方式，所述湿法球磨采用氧化锆球作为球磨介质，进行湿法球磨24h。As a preferred embodiment of the present invention, the wet ball milling uses zirconia balls as the ball milling medium, and performs wet ball milling for 24 hours.
本发明还提供上述陶瓷介质材料在电子元器件中的应用；所述电子元器件包括多层陶瓷电容器。The present invention also provides the application of the above-mentioned ceramic dielectric material in electronic components; the electronic components include multilayer ceramic capacitors.
作为本发明的优选实施方式，所述陶瓷介质材料在还原气氛中1200-1260℃下，烧结3-5h，退火后依次经过切割、封端处理得到多层陶瓷电容器。As a preferred embodiment of the present invention, the ceramic dielectric material is sintered at 1200-1260° C. for 3-5 hours in a reducing atmosphere, and after annealing, the multilayer ceramic capacitor is obtained by sequentially cutting and end-capping treatment.
作为本发明的优选实施方式，所述多层陶瓷电容器中陶瓷介质的晶粒尺寸为200-320nm。As a preferred embodiment of the present invention, the grain size of the ceramic dielectric in the multilayer ceramic capacitor is 200-320 nm.
作为本发明的优选实施方式，所述多层陶瓷电容器在25℃下的介电常数为5000-5600。As a preferred embodiment of the present invention, the dielectric constant of the multilayer ceramic capacitor at 25° C. is 5000-5600.
作为本发明的优选实施方式，所述多层陶瓷电容器在-55-85℃下，电容变化率介于±15％。As a preferred embodiment of the present invention, the multi-layer ceramic capacitor has a capacitance change rate of ±15% at -55-85°C.
作为本发明的优选实施方式，所述多层陶瓷电容器的平均击穿强度为100-125kV/mm。As a preferred embodiment of the present invention, the average breakdown strength of the multilayer ceramic capacitor is 100-125kV/mm.
作为本发明的优选实施方式，所述加速老化寿命测试结果为2.3-2.7h。As a preferred embodiment of the present invention, the accelerated aging life test result is 2.3-2.7h.
本发明通过共掺杂钛酸钡陶瓷介电材料在还原气氛中烧结制备的多层陶瓷电容器MLCC，具有100kV/mm以上的击穿强度，延缓了高温下的绝缘电阻劣化，加速老化寿命测试达到2.3h以上达到，此外其介电常数介于5000-5600之间，且能够满足X5R温度特性要求，即温度-55-85℃时，电容变化率在+15％到-15％之间。The multilayer ceramic capacitor MLCC prepared by sintering the co-doped barium titanate ceramic dielectric material in the reducing atmosphere in the present invention has a breakdown strength of more than 100kV/mm, delays the deterioration of insulation resistance under high temperature, and achieves the accelerated aging life test. 2.3h or more, in addition, its dielectric constant is between 5000-5600, and it can meet the requirements of X5R temperature characteristics, that is, when the temperature is -55-85℃, the capacitance change rate is between +15% and -15%.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
(1)本发明共掺杂钛酸钡陶瓷介电材料在还原气氛中烧结制备的多层陶瓷电容器击穿强度在100kV/mm以上，加速老化寿命测试达到2.3h以上，介电常数变化能够满足X5R要求。(1) The breakdown strength of the multilayer ceramic capacitor prepared by sintering the co-doped barium titanate ceramic dielectric material of the present invention in a reducing atmosphere is above 100kV/mm, the accelerated aging life test reaches above 2.3h, and the change in dielectric constant can satisfy X5R requirements.
(2)本发明提供的共掺杂钛酸钡陶瓷介电材料所用烧结助剂均为氧化物，种类多用量较少，成本较低且不含铅、汞等有害元素。(2) The sintering aids used in the co-doped barium titanate ceramic dielectric material provided by the present invention are all oxides, with various types and less dosage, low cost and no harmful elements such as lead and mercury.
(3)本发明制备的多层陶瓷电容器晶粒细且分布均匀，陶瓷层与贱金属内电极和外电极匹配良好，电极孔洞少无应力裂纹。(3) The multi-layer ceramic capacitor prepared by the invention has fine grains and uniform distribution, the ceramic layer is well matched with the base metal inner electrode and the outer electrode, and the electrode holes are few and free of stress cracks.
附图说明Description of drawings
图1为本发明实施例1的陶瓷介质材料的FESEM图。FIG. 1 is a FESEM image of the ceramic dielectric material of Example 1 of the present invention.
图2为本发明实施例2的陶瓷介质材料的FESEM图。FIG. 2 is a FESEM image of the ceramic dielectric material of Example 2 of the present invention.
图3为本发明实施例3的陶瓷介质材料的FESEM图。FIG. 3 is a FESEM image of the ceramic dielectric material of Example 3 of the present invention.
图4为本发明实施例4的陶瓷介质材料的FESEM图。FIG. 4 is a FESEM image of the ceramic dielectric material of Example 4 of the present invention.
图5为根据图1的FESEM图统计的实施例1的陶瓷晶粒尺寸分布图。FIG. 5 is a graph showing the size distribution of ceramic grains of Example 1 according to the statistics of the FESEM image of FIG. 1 .
图6为根据图2的FESEM图统计的实施例2的陶瓷晶粒尺寸分布图。FIG. 6 is a graph showing the size distribution of ceramic grains of Example 2 according to the statistics of the FESEM image of FIG. 2 .
图7为根据图3的FESEM图统计的实施例3的陶瓷晶粒尺寸分布图。FIG. 7 is a graph showing the size distribution of ceramic grains of Example 3 according to the statistics of the FESEM image of FIG. 3 .
图8为根据图4的FESEM图统计的实施例4的陶瓷晶粒尺寸分布图。FIG. 8 is a graph showing the size distribution of ceramic grains of Example 4 according to the statistics of the FESEM image of FIG. 4 .
图9为本发明实施例1制得的MLCC试样介电常数变化率与温度的关系图。FIG. 9 is a graph showing the relationship between the change rate of the dielectric constant of the MLCC sample prepared in Example 1 of the present invention and the temperature.
图10为本发明实施例2制得的MLCC试样介电常数变化率与温度的关系图。10 is a graph showing the relationship between the change rate of the dielectric constant of the MLCC sample prepared in Example 2 of the present invention and the temperature.
图11为本发明实施例3制得的MLCC试样的电容常数变化率与温度的关系图。11 is a graph showing the relationship between the change rate of the permittivity constant and the temperature of the MLCC sample prepared in Example 3 of the present invention.
图12为本发明实施例4制得的MLCC试样的电容常数变化率与温度的关系图。12 is a graph showing the relationship between the change rate of the permittivity constant and the temperature of the MLCC sample prepared in Example 4 of the present invention.
图13为本发明实施例1制得的MLCC试样的击穿强度韦伯分布结果图。13 is a graph showing the results of the Weber distribution of breakdown strength of the MLCC sample prepared in Example 1 of the present invention.
图14为本发明实施例2制得的MLCC试样的击穿强度韦伯分布结果图。14 is a graph showing the results of the Weber distribution of breakdown strength of the MLCC sample prepared in Example 2 of the present invention.
图15为本发明实施例3制得的MLCC试样的击穿强度韦伯分布结果图。15 is a graph showing the results of the Weber distribution of breakdown strength of the MLCC sample prepared in Example 3 of the present invention.
图16为本发明实施例4制得的MLCC试样的击穿强度韦伯分布结果图。16 is a graph showing the results of the Weber distribution of breakdown strength of the MLCC sample prepared in Example 4 of the present invention.
图17为本发明实施例1加速老化测试结果图。FIG. 17 is a graph showing the results of an accelerated aging test in Example 1 of the present invention.
图18为本发明实施例2加速老化测试结果图。FIG. 18 is a graph showing the results of an accelerated aging test in Example 2 of the present invention.
图19为本发明实施例3加速老化测试结果图。FIG. 19 is a graph showing the results of an accelerated aging test in Example 3 of the present invention.
图20为本发明实施例4加速老化测试结果图。FIG. 20 is a graph showing the results of an accelerated aging test in Example 4 of the present invention.
具体实施方式Detailed ways
本发明的目的在于制备一种陶瓷介质材料，所述材料的主体材料为BaTiO3，掺杂材料包括SiO2、CaO、V2O5、ZrO2和稀土元素的氧化物；所述稀土元素的氧化物包括Sc2O3、Sm2O3、Dy2O3、Ho2O3中的至少两种；按摩尔百分比计，BaTiO3的添加量为93.5～95mol％；掺杂材料的总添加量为4.6～7mol％。其中，主体材料BaTiO3的颗粒尺寸为180～240nm。The purpose of the present invention is to prepare a ceramic dielectric material, the main material of which is BaTiO 3 , and the doping material includes SiO 2 , CaO, V 2 O 5 , ZrO 2 and oxides of rare earth elements; Oxides include at least two of Sc 2 O 3 , Sm 2 O 3 , Dy 2 O 3 , Ho 2 O 3 ; the addition amount of BaTiO 3 is 93.5-95 mol % in mole percent; the total addition of doping materials The amount is 4.6 to 7 mol%. The particle size of the host material BaTiO 3 is 180-240 nm.
下述实施例中，共掺杂钛酸钡陶瓷介电材料和多层陶瓷电容器MLCC制备过程如下：In the following embodiments, the preparation process of co-doped barium titanate ceramic dielectric material and multilayer ceramic capacitor MLCC is as follows:
(1)选取颗粒尺寸在180-240nm的高纯BaTiO3粉体按比例与各种掺杂材料混合，采用氧化锆球作为球磨介质，置于球磨机中，进行湿法球磨24h，球磨完毕后进行干燥，得到陶瓷介电材料粉末。(1) Select high-purity BaTiO 3 powder with a particle size of 180-240 nm and mix it with various doping materials in proportion, using zirconia balls as the ball milling medium, placing them in a ball mill, and performing wet ball milling for 24 hours. After drying, a ceramic dielectric material powder is obtained.
(2)制备MLCC试样：取上述方法获得的陶瓷介电材料粉末，制成浆料，流延成1.5μm的膜片，再经过电极印刷、叠层、压制、切割形成具有一定形状和尺寸的生坯。其中，采用镍浆作为内电极，叠层数为300层。将生坯片在还原气氛(1.1％H2+98.9％N2)中1200-1260℃条件下，烧结35h，随后降至900-1050℃进行再氧化退化处理1.5h，再降至25℃完成烧结，形成独石结构瓷体。随后在瓷体两端通过沾铜的方式沾上铜浆，再烧结形成与瓷体牢固结合的铜电极，再在铜电极的表面电镀上镍层，第二次电镀上锡层，制得MLCC试样。(2) Preparation of MLCC samples: take the ceramic dielectric material powder obtained by the above method, make a slurry, cast it into a 1.5 μm membrane, and then go through electrode printing, lamination, pressing and cutting to form a certain shape and size. 's green body. Among them, nickel paste was used as the internal electrode, and the number of layers was 300 layers. The green sheets were sintered at 1200-1260°C in a reducing atmosphere (1.1%H 2 +98.9%N 2 ) for 35h, then lowered to 900-1050°C for re-oxidation and degradation treatment for 1.5h, and then lowered to 25°C to complete Sintered to form a monolithic ceramic body. Then, the two ends of the porcelain body are dipped with copper paste by dipping copper, and then sintered to form a copper electrode that is firmly bonded to the porcelain body. Then, a nickel layer is electroplated on the surface of the copper electrode, and a tin layer is electroplated for the second time to obtain MLCC. sample.
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below with reference to specific embodiments.
实施例1Example 1
本实施例中，主体材料BaTiO3粉体的颗粒尺寸为180nm，表1为实施例1各组分的配方表。In this example, the particle size of the host material BaTiO 3 powder is 180 nm, and Table 1 is the formula table of each component in Example 1.
表1实施例1的配方表The formula table of table 1
实施例2Example 2
本实施例中，主体材料BaTiO3粉体的颗粒尺寸为240nm，表2为实施例2各组分的配方表。In this example, the particle size of the host material BaTiO 3 powder is 240 nm, and Table 2 is the formula table of each component in Example 2.
表2实施例2的配方表The formula table of table 2
实施例3Example 3
本实施例中，主体材料BaTiO3粉体的颗粒尺寸为240nm，表3为实施例3各组分的配方表。In this example, the particle size of the host material BaTiO 3 powder is 240 nm, and Table 3 is the formula table of each component in Example 3.
表3实施例3的配方表The formula table of table 3 embodiment 3
实施例4Example 4
本实施例中，主体材料BaTiO3粉体的颗粒尺寸为180nm，表3为实施例3各组分的配方表。In this example, the particle size of the host material BaTiO 3 powder is 180 nm, and Table 3 is the formula table of each component in Example 3.
表4实施例4的配方表The formula table of table 4 embodiment 4
本发明较佳实施例1、实施例2和实施例3，对比实施例4的扫描电子显微镜(FESEM)表征结果分别如图1、图2、图3和图4所示，实施例1、2、3制得的样品致密度良好，没有明显孔洞。The scanning electron microscope (FESEM) characterization results of the
根据SEM图统计的陶瓷晶粒尺寸分布如图5、图6、图7、图8所示(其中，实施例1统计晶粒157个，实施例2统计晶粒165个，实施例3统计晶粒154个，实施例4统计晶粒171个)：本发明实施例1、2、3制得的MLCC的陶瓷晶粒尺寸分布更均匀，平均晶粒尺寸为240nm、310nm和320nm，实施例4出的平均晶粒尺寸为200nm，但少数晶粒出现了异常长大，尺寸达800nm以上，均匀性较差。The size distribution of ceramic grains according to the SEM image is shown in Figure 5, Figure 6, Figure 7, Figure 8 (among which, Example 1 counts 157 crystal grains, Example 2 counts 165 crystal grains, and Example 3 counts crystal grains 154 grains, 171 grains in Example 4): The ceramic grain size distribution of the MLCC prepared in Examples 1, 2, and 3 of the present invention is more uniform, and the average grain size is 240 nm, 310 nm and 320 nm, Example 4 The average grain size is 200nm, but a few grains grow abnormally, the size is over 800nm, and the uniformity is poor.
对比本发明实施例1、2、3、4制得的MLCC试样的电容常数变化率与温度的关系，结果如图9、图10、图11、图12所示：在温度-55-85℃之间，电容变化率介于+15％到-15％之间，基本满足EIA的X5R要求。Comparing the relationship between the change rate of the permittivity constant and the temperature of the MLCC samples prepared in Examples 1, 2, 3, and 4 of the present invention, the results are shown in Figure 9, Figure 10, Figure 11, and Figure 12: Between ℃, the capacitance change rate is between +15% and -15%, which basically meets the X5R requirements of EIA.
对比本发明实施例1、2、3、4制得的MLCC试样的击穿强度韦伯分布结果如图13、图14、图15、图16所示：本发明较佳实施例1、2、3制得的样品提升了耐压特性，平均击穿强度能达到100kV/mm以上，而对比实施例4击穿强度低于60kV/mm，较佳实施例相比其提升了约2倍。Figure 13, Figure 14, Figure 15, Figure 16 show the results of the Weber distribution of the breakdown strength of the MLCC samples prepared in Examples 1, 2, 3, and 4 of the present invention: The samples prepared in 3 have improved withstand voltage characteristics, and the average breakdown strength can reach more than 100kV/mm, while the breakdown strength of Comparative Example 4 is lower than 60kV/mm, which is about 2 times higher than that of the preferred embodiment.
为了拓展本发明的应用领域，特别测试了实施例1、2、3、4，制得的的样品在150℃下，从2kV/mm开始，每0.25h增加2kV/mmm的直流电压的加速老化测试中的使用寿命，结果如图17、图18、图19、图20所示。较佳实施例1、2、3的老化测试寿命也相对对比实施例4提高了约1.5倍。In order to expand the application field of the present invention, Examples 1, 2, 3, and 4 were specially tested, and the prepared samples were accelerated aging at 150°C, starting from 2kV/mm, and increasing DC voltage of 2kV/mmm every 0.25h. The service life in the test, the results are shown in Figure 17, Figure 18, Figure 19, and Figure 20. The aging test life of the
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。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that, The technical solutions of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention.
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