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

doi:10.15541/jim20210718

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 12

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

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

Fig. 2 Temperature dependent ε for different samples

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

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

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

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

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

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	-	-

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

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

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

References 28

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

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