BaTiO3-Based Multilayers with Outstanding Energy Storage

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BaTiO3-Based Multilayers with Outstanding Energy Storage Performance for High Temperature Capacitor Applications Wenbo Li, Di Zhou, Ran Xu, Da-Wei Wang, Jinzhan Su, Li-Xia Pang, Wenfeng Liu, and Guo-Hua Chen ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.9b00664 • Publication Date (Web): 09 Jul 2019 Downloaded from pubs.acs.org on July 19, 2019

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ACS Applied Energy Materials

BaTiO3-Based Multilayers with Outstanding Energy Storage Performance for High Temperature Capacitor Applications Wen-Bo Li,a,b Di Zhou, a,b Ran Xu,a Da-Wei Wang,c Jin-Zhan Su,d Li-Xia Pang,e Wen-Feng Liu,band Guo-Hua Chenf aElectronic

Materials Research Laboratory, Key Laboratory of the Ministry of Education &

International Center for Dielectric Research, School of Electronic and Information Engineering, Xi’an Jiaotong University, Xi'an 710049, Shaanxi, China bState

Key Laboratory of Electrical Insulation and Power Equipment, Xi'an Jiaotong University, Xi’an 710049, Shaanxi, China

cDepartment

of Materials Science and Engineering, University of Sheffield, Sheffield S1 3JD, United Kingdom

dInternational

Research Centre for Renewable Energy, State Key Laboratory of

Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi’an, Shaanxi 710049, China

ACS Paragon Plus Environment

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ACS Applied Energy Materials 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

eMicro-optoelectronic

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Systems Laboratories, Xi’an Technological University, Xi’an 710032, Shaanxi, China

fGuangxi

Key Laboratory of Information Materials, Guilin University of Electronic

Technology, Guilin 541004, P.R. China Corresponding

author. E-mail address: [email protected]

KEYWORDS: Ceramic; BaTiO3; Multilayer ceramic capacitors; Energy storage property ABSTRACT

With the ultrahigh power density and fast charge-discharge capability, dielectric capacitor is an important way to meet the fast increase in the demand for energy storage system such as pulsed power systems (PPS). BaTiO3-based capacitor is considered as one of the candidates for PPS due to their high permittivity. However, with the continuous miniaturization of PPS, the demand further increases in energy density and thermal stability of BaTiO3-based capacitors. Thus, this work describes a new high performance multilayer ceramic capacitors (MLCC) of BaTiO3-xBi(Li0.5Nb0.5)O3 (BT-xBLN) (0.0 ≤ x ≤ 1.0) for PPS. Based on the XRD and dielectric constant of BTxBLN (0.0 ≤ x ≤ 1.0) ceramics, all compositions exhibited an average perovskite structure


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(tetragonal phase: 0.0 ≤ x < 0.05 and pseudocubic phase: 0.05 ≤ x < 0.4) and multiple phase (0.4 ≤ x < 1.0). For example, the 0.90BaTiO3-0.10Bi(Li0.5Nb0.5)O3 multilayer ceramics capacitors were characterized by charge efficiency (η ≥ 91.5%), discharge energy density (Ue ~ 4.5 J cm-3), breakdown strength (Eb > 450 kV cm-1) and good thermal stability, demonstrating their potential in PPS. This work makes breakthroughs in BaTiO3-based capacitor materials with high Ue and adds a new member to the BaTiO3-based dielectric capacitor material family for energy storage field.

1. Introduction Nowadays, dielectric capacitors become an extremely promising candidates and widely used in PPS due to high Ue and the capability of ultrafast chargingdischarging (τ0.9 < 1 μs).1-5 High performance capacitors with high Ue, good thermal stability and high η would contribute to reduce the volume and weight of PPS. BaTiO3based solid solution capacitors with the ultrahigh power density is considered as one of the most promising candidates for PPS.6-10 However, most BaTiO3-based solid solution capacitors cannot achieve higher energy density to come up to the increasing demands for continuous miniaturization of PPS.11-20 So it is important to improve Ue of BaTiO3-


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based solid solution capacitors and many researchers have made great efforts to increase Ue of BaTiO3-based solid solution capacitors.21-23 The Ue of linear dielectric is determined by dielectric constant (εr) and electric field (E):14

U e  0.5 0 r E 2 ,

(1)

where ε0 = 8.85 × 10-12 F m-1. It is well known that Ue of antiferroelectric (AFE) and ferroelectric (FE) ceramics is calculated by the integral:14 Ps

U   EdP ,

(2)

0

Ps

U e   EdP ,

(3)

Pr



Ue 100% U

(4)

where Ps, Pr, E and η are saturated polarization, remnant polarization, electric field and energy efficiency, respectively. Improving breakdown field strength of BaTiO3-based ceramics can effectively increase the energy density for energy storage application. For example, the BSTMMgO composite ceramics are formed by adding high breakdown field strength oxides to


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BST ceramics with a greatly enhanced breakdown field strength of 300 kV cm-1, Ue about 2 J cm-3 with η ~ 88.6%.24,25 However, the permittivity of barium titanate is decreased by low permittivity oxides, which inhibited energy density of barium titanate. Then, enlarging the values of the Ps-Pr is effectively enhanced the energy-storage density. The slim P-E loop of BaTiO3-based relaxor ferroelectrics BaTiO3-Bi(MN)O3 or BaTiO3-BiRO3 ceramics show higher Ps and near zero Pr. The studies show that Ue of 0.91BaTiO3-0.09BiYbO3 ceramics, BT-BMT ceramics and BT-BMN ceramics can be improved from 1 to 2 J cm-3.26-33 For the BaTiO3-BiRO3 systems, 0.7BaTiO3-0.3BiScO3 capacitors have been studied with high Ue ~ 6.1 J cm-3 under 73 kV mm-1.34 BiFeO3BaTiO3 multilayers demonstrated significant improvement in performance (Wrec = 6.74 J cm-3).35 All results indicated that BaTiO3-Bi(MN)O3 or BaTiO3-BiRO3 with higher Ps, lower Pr and low energy loss are promising candidate system. In this paper, 0.90BT0.10BLN multilayer ceramics capacitors were prepared by tape-casting method and achieve significantly enhanced high Ue (> 4.5 J cm-3) and η (> 91.5%) with good thermal stability up to 160 oC.


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2. Results and discussion

2.1. Structure analysis Fig. 1 shows XRD profiles and lattice parameters of BT-xBLN (0.0 ≤ x < 0.2) samples. In this work, when the x value is in the range of 0 to 0.04, phase of BT-xBLN was tetragonal phase. When the value of x is between 0.05 and 0.2, pseudo-cubic phase was formed in the sample. Fig. 1a also shows that the diffraction peak in XRD pattern moves to low angle with the increase of BLN content, which is due to the increase of cell volume. Lattice parameters of the BT-xBLN (0.00 ≤ x ≤ 0.20) ceramics as function of the BLN content in Fig. 1b. The cell parameter and volume for pure BT (x = 0.0) ceramics were calculated as a = 3.9708(1) Å and c = 5.7129(1) Å and volume=63.92 Å3. The results indicate that phase of BT-xBLN sample has changed from tetragonal to pseudo-cubic with the increase of BLN content. From Fig. 1b, the phase of the BT-BLN changes from tetragonal phase (P4mm, 0.0 ≤ x < 0.05) to pseudocubic phase (Pm-3m, 0.05 ≤ x ≤ 0.20) with x value increased. Fig. S1 shows XRD profiles of BT-xBLN (0.1 ≤ x ≤ 1.0) samples. BT-xBLN (0.00 ≤ x ≤ 0.20) ceramics exhibited perovskite structure. The well-defined sharp peaks of BT can be indexed to a


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tetragonal phase with P4mm (99) symmetry. The phase of BT-xBLN changed from tetragonal phase for BT ceramics to pseudo-cubic phase for 0.04 ≤ x ≤ 0.2 by enlarging patterns at about 45°. For compositions 0.4 ≤ x < 1.0, a composite multiple phase was formed. In the BT-BLN system, the following substitution is expected,

BaTiO3 Bi(Li0.5Nb0.5)O3   BiBa• + 3Oox + (LiNb)Tiʼ

(5)

For the ABO3 perovskite structure in 12 coordinate environment, the equivalent ionic radii of Bi3+ (1.35 Å) is smaller than that of Ba2+ (1.61 Å). The equivalent ionic radii of (Li0.5Nb0.5)3+ is 0.70 Å.36 It can be seen that the equivalent ionic radii of Ti4+ (0.605 Å) is similar to that of (Li0.5Nb0.5)3+, it is understandable that the (Li0.5Nb0.5)3+ ion may enter into the Ti site. It is believed that (Li0.5Nb0.5)3+ ions and Bi3+ ions enter Ti site and Ba site of BaTiO3, respectively. The phase of samples is multiple phase with 0.4 ≤ x < 1.0. The structure changed to a multiphase bismuth layered structure at x = 1.0. Fig. 1c shows P-E loops of BT-xBLN (x = 0.01, 0.04, 0.06, 0.08, 0.1, 0.2) samples at 10 Hz and 85 kV cm1.

When the x value increases from 0 to 0.2, the shape of P-E loops change from a fat

shape to a thin shape and then to a linear shape in Fig. 1c. The change of the P-E loops


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showed that the ferroelectric properties of the BT-xBLN samples gradually weaken with the increase of x value from 0 to 0.2.

Fig. 2 shows the microstructure images of sintered BT-xBLN (0.01 ≤ x ≤ 0.2) ceramics. It exhibits a dense microstructure, no visible porosity and a grain size that gradually grew from ~1μm to ~2 μm for BT-xBLN (0.01 ≤ x ≤ 0.2) ceramics.

2.2. Dielectric properties Fig. 3 and Fig. S2 show dielectric permittivity (εr) and loss (tanδ) of BT-xBLN (x= 0.01, 0.04, 0.06, 0.08, 0.1, 0.2) samples at frequencies from 1kHz to 0.1 MHz in the wide temperature range from 25 to 300 oC. In this study, it shows that one dielectric peak can be observed from 25 oC to 300 oC. It is indicated that addition of BLN can obviously decrease phase temperature from tetragonal to cubic (TO-T) in BT-based ceramics in Fig. 3. So the dielectric peak position slightly moved in the direction of low temperature with the addition content of BLN exceeds x = 0.04. It also can be seen that the Tm decreases from 120 oC for BT ceramic to 100 and 60 oC for the sample of 0.99BT-0.01BLN and 0.96BT-0.04BLN, respectively. The permittivity at about Tm also


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decreases from 6500 for 0.99BT-0.01BLN ceramic to 3800 for 0.96BT-0.04BLN ceramic. Fig.3 shows the diffuse phase transition in BT-BLN samples. Fig. S3 (Supporting Information) shows the variation of εr with temperature and frequencies for the BT-BLN ceramics. In this study, the relaxor behaviour can be explained by the Ba and Ti site were replaced by Bi3+ and (Li0.5Nb0.5)3+. In addition, Tm and the dielectric constant at this temperature found to decrease with the BLN content increase when x ≤ 0.04. From Fig. S3, one can see that εr of the BT-BLN ceramics decrease while tanδ increase as temperature increased. With the content of BLN increases, εr of samples decrease from 4000 for 0.96BT-0.04BLN ceramic to 600 for 0.80BT-0.20BLN ceramic and tanδ keep quite low. In addition, previous studies also reported that the showed that Bi-based compound has low sintering temperature and loss.24-26 The experimental results show that barium titanate based ceramics for energy storage application, high breakdown field strength and moderate dielectric constant are the conditions for obtaining high energy storage density.

2.3. Energy storage properties


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The Eb analyzed by using a Weibull distribution function for BT-xBLN ceramics is shown in Fig. 4. From Fig. 4, near Eb of BT-xBLN samples increases from 195 to 235 kV cm-1 with the increases of BLN content. The maximum Eb of 235 kV cm-1 can be observed in 0.90BT-0.10BLN ceramic. Compare with pure BT, it can be observed that the breakdown strength of BT-BLN ceramic increases remarkably with BLN addition when x ≤ 0.2. The studies have showed that some factors such as the grain size of samples have an effect on the breakdown strength.20 It indicates that BT-xBLN (0.04 ≤ x ≤ 0.20) ceramics have dense microstructure and high breakdown strength.

Fig. 5 shows energy storage properties, Pr and Ps of BT-xBLN (0.04 ≤ x ≤ 0.20) ceramics under a series of electric fields. The values of the Ps, Pr, Ue and η of sampls are studied by P-E loops. Unipolar P-E loops of the BT-xBLN (0.04 ≤ x ≤ 0.20) ceramics are measured under a series of electric fields. From Fig. 5, the P-E loops get fat with electric field the increases. Fig. 5 shows Pr and Ps of BT-xBLN (x = 0.04, 0.06, 0.08, 0.1, 0.2) depending on the electric field. When electric field increase to 240 kV cm-1, both Pr and Ps of 0.9BT-0.1BLN increase to 1.19 and 19.77 μC cm-2 at 240 kV cm-1,


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respectively. Maybe polarization mechanism lead to the differences. Fig. 5 shows the Ue and the η depending on electric field that with the increase of E, the Ue increases and the η decreases. When the E increases from 40 to 235 kV cm-1, the Ue of 0.90BT0.10BLN increases from 0.21 to 1.8 J cm-3. The η is decided by the ratio of Ue and U. When the applied electric field is in the range of 40 to 250 kV cm-1, the η remains a high efficiency (> 88%). From this work, BT-xBLN (0.04 ≤ x ≤ 0.20) ceramics exhibit high applied electric field (> 250 kV cm-1), Ue (> 1.8 J cm-3) and η (> 80%).

Fig. 6 shows the change of Ps, Pr, Ue and η of BT-xBLN (0.04 ≤ x ≤ 0.20) creamics with the content of BLN compound. The content of BLN with low permittivity (

BaTiO3-Based Multilayers with Outstanding Energy Storage

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