改性(Sr,Ca)TiO3基储能陶瓷介电及MLCC性能研究

doi:10.15541/jim20210718

无机材料学报 ›› 2022, Vol. 37 ›› Issue (9): 976-982.DOI: 10.15541/jim20210718 CSTR: 32189.14.10.15541/jim20210718

所属专题：【信息功能】纪念殷之文先生诞辰105周年虚拟学术专辑

改性(Sr,Ca)TiO₃基储能陶瓷介电及MLCC性能研究

陈永虹¹(), 林志盛¹, 张子山¹, 陈本夏¹, 王根水²()

1.福建火炬电子科技股份有限公司, 泉州 362000
2.中国科学院上海硅酸盐研究所, 上海 200050

收稿日期:2021-11-22 修回日期:2021-12-23 出版日期:2022-09-20 网络出版日期:2022-06-16
通讯作者: 王根水, 研究员. E-mail: genshuiwang@mail.sic.ac.cn
作者简介:陈永虹(1981-), 男, 工程师. E-mail: chenyh@torch.cn
基金资助:
国家自然科学基金重点项目(U2002217)

Dielectric and MLCC Property of Modified (Sr,Ca)TiO₃ Based Energy Storage Ceramic

CHEN Yonghong¹(), LIN Zhisheng¹, ZHANG Zishan¹, CHEN Benxia¹, WANG Genshui²()

1. Fujian Torch Electron Technology Co., Ltd, Quanzhou 362000, China
2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2021-11-22 Revised:2021-12-23 Published:2022-09-20 Online:2022-06-16
Contact: WANG Genshui, professor. E-mail: genshuiwang@mail.sic.ac.cn
About author:CHEN Yonghong (1981-), male, engineer. E-mail: chenyh@torch.cn
Supported by:
National Natural Science Foundation of China(U2002217)

摘要/Abstract

摘要：

工业级脉冲储能多层瓷介电容器(MLCC)是现阶段国内研制和生产电子启动装置的重要元器件, 针对国内主要有机薄膜电容器尺寸大、寿命短、可靠性较低的不足, 本研究采用传统固相反应法, 制备了SrTiO₃和CaTiO₃基的脉冲储能介质陶瓷材料, 研究了微量助烧剂掺杂, 以及Sr²⁺/Ca²⁺相互掺杂对陶瓷材料的介电性能的影响, 并进一步制备和研究了以(Sr,Ca)TiO₃为基体MLCC性能。实验结果表明: 通过加入质量分数1.0%的助烧剂, 引入微量Bi³⁺ 可取代Sr²⁺, 提高了SrTiO₃材料的介电常数, 而Bi³⁺对CaTiO₃基材料的介电性能无明显影响; Mn元素有效抑制高温烧结中Ti⁴⁺的还原, 降低介电损耗; 加入助烧剂有效降低瓷粉的烧结温度, 提高材料的致密性。(Sr_xCa_1-_x)TiO₃体系的MLCC可保持较高的介电常数和较低的介电损耗, 当 x=0.4 时, 其介电损耗tanδ=1.8×10^-4, 击穿强度为59.38 V/μm, 高低温放电电流变化率为±7%, 放电稳定, 在常温和高温(125 ℃)下经1000次循环充放电实验均未失效, 是一种在不同电场强度下具有相对较优的容量稳定性以及较高可靠性的脉冲特性(Sr,Ca)TiO₃基电容器陶瓷介质材料。

关键词: (Sr,Ca)TiO₃, 瓷粉, 脉冲, 多层瓷介电容器

Abstract:

Industrial pulse energy storage multilayer ceramic capacitors (MLCC) are important components for the development and production of electronic starting devices in China. In view of the shortcomings of large size, short life and low reliability of organic film capacitors, SrTiO₃ and CaTiO₃ based pulse energy storage dielectric ceramics were prepared by traditional solid-state reaction method in this study. The effects of sintering aid doping and Sr²⁺/Ca²⁺ mutual doping on the dielectric properties of ceramic materials were studied, and the property of MLCC based on (Sr,Ca)TiO₃ were further prepared and investigated. The results show that the dielectric constant of SrTiO₃ materials can be improved by adding the sintering aid with a mass ratio of 1.0%, such as the introduction of trace Bi³⁺, while Bi³⁺ has no obvious effect on the CaTiO₃ based materials. Doping of Mn element can effectively inhibit the reduction of Ti⁴⁺ during high-temperature sintering and reduce dielectric loss. Moreover, the addition of sintering aid can effectively reduce the sintering temperature of ceramic powder and improve the compactness of the material. The MLCC prepared from (Sr_xCa_1-_x)TiO₃ material can maintain high dielectric constant and low dielectric loss, at x=0.4, the dielectric loss tanδ=1.8×10^-4, the breakdown strength is 59.38 V/μm, and the high and low temperature discharge current change rate is ±7%, which shows good discharge stability. In addition, no matter it is at room temperature or high temperature (125 ℃), the sample has no failure after 1000 cycles of discharge experiment. Therefore, the as-obtained (Sr, Ca)TiO₃ based ceramic dielectric material can be a promising pulse capacitor with relatively excellent capacity stability and high reliability under different electric field strength.

Key words: (Sr,Ca)TiO₃, ceramic powder, pulse, multilayer ceramic capacitor

中图分类号:

TQ174

陈永虹, 林志盛, 张子山, 陈本夏, 王根水. 改性(Sr,Ca)TiO₃基储能陶瓷介电及MLCC性能研究[J]. 无机材料学报, 2022, 37(9): 976-982.

CHEN Yonghong, LIN Zhisheng, ZHANG Zishan, CHEN Benxia, WANG Genshui. Dielectric and MLCC Property of Modified (Sr,Ca)TiO₃ Based Energy Storage Ceramic[J]. Journal of Inorganic Materials, 2022, 37(9): 976-982.

图/表 12

表1 6878多层瓷介电容器外形尺寸

Table 1 Overall dimensions of 6878 multilayer ceramic capacitor

Specifications	L/mm	W/mm	T_max/mm	t/mm
6878	17.30±0.80	19.80±0.80	7.80	1.10±0.70

图1 电容器的结构图(a, b)与等效电路示意图(c)

Fig. 1 Structure (a, b) and equivalent circuit diagram (c) of the capacitor

图2 不同配方样品的介电常数随温度的变化曲线

Fig. 2 Temperature dependent ε for different samples

表2 不同配方样品的基本电性能

Table 2 Electrical properties of different samples

Sample	ε	tanδ/(×10^-4)
SrTiO₃	262	6.4
CaTiO₃	159	6.0
SrTiO₃+dopant	388	34.7
CaTiO₃+dopant	157	4.6

表3 不同Sr/Ca比(SrxCa1-x)TiO3的基本电性能

Table 3 Electrical properties of (SrxCa1-x)TiO3 with different Sr/Ca ratios

Sample	ε	tanδ/(×10^-4)
x=1	388	34.7
x=0.9	348	10.5
x=0.8	303	12.8
x=0.7	298	9.4
x=0.6	299	8.7
x=0.5	282	3.7
x=0.4	249	3.0
x=0.3	218	2.6
x=0.2	202	3.5
x=0.1	181	3.3
x=0	157	4.6

图3 不同Sr/Ca比(SrxCa1-x)TiO3的电容温度系数(TCC)曲线

Fig. 3 Capacitance temperature coefficient of (SrxCa1-x)TiO3 with different Sr/Ca ratios

图4 (Sr0.4Ca0.6)TiO3瓷粉的SEM照片(a~c)和EDS元素分布图(d~g)

Fig. 4 SEM images (a-c), EDS elemental maps (d-g) of the (Sr0.4Ca0.6)TiO3 ceramic powder

表4 不同Sr/Ca比瓷介粉料制备MLCC的基本电性能

Table 4 Electrical properties of MLCC prepared from ceramic materials with different Sr/Ca ratios

Samples	C/nF	tanδ/ (×10^-4)	TCC/(×10^-6, K^-1)		BDV/V
Samples	C/nF	tanδ/ (×10^-4)	-55 ℃	125 ℃	BDV/V
x=0.4	100.87	1.8	-2464.4	-1963.2	6650
x=0.5	100.29	2.3	-3118.2	-2031.6	5690

表5 不同Sr/Ca比瓷介粉料制备MLCC的放电电流及其与商用MLCC的对比

Table 5 Discharge current of MLCC prepared from ceramic powder with different Sr/Ca ratios and comparison with commercial MLCC

T/℃ Sample		-45	-35	25	85	125
x=0.4	Current/A	4303	4215	4039	3864	3732
x=0.4	Rate/%	6.5	4.4	-	-4.3	-7.6
x=0.5	Current/A	4445	4445	4193	4025	3774
x=0.5	Rate/%	6.0	6.0	-	-4.0	-10.0
Commercial MLCC^(a)	Current/A	-	-	3500	-	-

图5 不同Sr/Ca比瓷介粉料制备MLCC的电场与容量变化关系曲线(a)及寿命实验(b)

Fig. 5 Relationship between electric field and capacity change (a), life test (b) of MLCC prepared from ceramic powder with different Sr/Ca ratios

图6 (Sr0.4Ca0.6)TiO3瓷粉制备的MLCC的SEM照片(a, b)和DPA分析(c, d)

Fig. 6 SEM images (a, b) and DPA analysis (c, d) of MLCC prepared by (Sr0.4Ca0.6)TiO3 ceramic powder

表6 (Sr0.4Ca0.6)TiO3基瓷粉制备的MLCC循环充放电试验

Table 6 Cyclic discharge test of MLCC prepared by (Sr0.4Ca0.6)TiO3 based ceramic powder

Sample	Voltage/V	T/℃	Discharge times	Result
x=0.4	4000	25	1000	No failure
x=0.4	4000	125	1000	No failure

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改性(Sr,Ca)TiO₃基储能陶瓷介电及MLCC性能研究

Dielectric and MLCC Property of Modified (Sr,Ca)TiO₃ Based Energy Storage Ceramic

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