CN116803949B - Sodium niobate-based antiferroelectric ceramic material, preparation method thereof and capacitor - Google Patents
Sodium niobate-based antiferroelectric ceramic material, preparation method thereof and capacitor Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 189
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003990 capacitor Substances 0.000 title claims abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 95
- 239000000126 substance Substances 0.000 claims abstract description 26
- 239000000919 ceramic Substances 0.000 claims description 115
- 239000002994 raw material Substances 0.000 claims description 36
- 238000000498 ball milling Methods 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 23
- 238000005245 sintering Methods 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 14
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 11
- 238000009694 cold isostatic pressing Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000003989 dielectric material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000004146 energy storage Methods 0.000 abstract description 40
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 100
- 230000005684 electric field Effects 0.000 description 36
- 230000007704 transition Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 17
- 150000001768 cations Chemical class 0.000 description 16
- 239000012535 impurity Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 11
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- 238000011160 research Methods 0.000 description 4
- 102100028292 Aladin Human genes 0.000 description 3
- 101710065039 Aladin Proteins 0.000 description 3
- 229910019792 NbO4 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005620 antiferroelectricity Effects 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 229910001219 R-phase Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910020923 Sn-O Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
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- 231100000701 toxic element Toxicity 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention provides a sodium niobate-based antiferroelectric ceramic material, a preparation method thereof and a capacitor, and belongs to the technical field of energy storage materials. The chemical formula of the ceramic material is as follows: (Na 1‑xK0.5xBi0.5x)(Nb1‑xSnx)O3, wherein x=4-10%, or (Na 0.94‑ 3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, wherein y=0.5-2%, or (Na 0.94‑yLayK0.03Bi0.03)(Nb0.94‑0.4ySn0.06)O3, wherein y=0.5-2%) the antiferroelectric stability of the ceramic material is high, a double ferroelectric hysteresis loop is realized, and thus the energy storage performance of the ceramic material is improved, the ceramic materials (Na 0.94‑ 3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 and (Na 0.94‑ yLayK0.03Bi0.03)(Nb0.94‑0.4ySn0.06)O3, wherein La 3+ is substituted (Na + in Na 0.94K0.03Bi0.03)(Nb0.94Sn0.06)O3, the aliovalent ion La 3+ is introduced, and simultaneously, a vacancy is introduced at Na + or Nb 5+), the stability of the field ferroelectric phase is broken, and the energy storage performance of the ceramic material is further improved.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a sodium niobate-based antiferroelectric ceramic material, a preparation method thereof and a capacitor.
Background
Antiferroelectric materials are attractive materials due to their characteristic electric field induced antiferroelectric-ferroelectric phase transitions, which are related to the small energy difference between the antiferroelectric phase and the ferroelectric phase. Antiferroelectric-ferroelectric phase transitions have enabled important applications for antiferroelectric materials in both storage capacitors, large strain drives and solid state refrigerators, which benefit from their associated dual hysteresis, large volume expansion and large electrothermal effects, respectively. However, most of antiferroelectric ceramic materials with excellent performance are lead zirconate (PbZrO 3) based perovskite materials at present and contain toxic element Pb. Therefore, the development of high performance lead-free antiferroelectric ceramic materials is critical for future dielectric energy storage applications.
Among the lead-free antiferroelectric ceramic materials known to date are silver niobate AgNbO 3 (AN) -based ceramic material [1-4,5,6,7-12] and sodium niobate NaNbO 3 (NN) -based ceramic material [13,14,15,16-18]. Wherein the energy storage performance of the AN-based antiferroelectric ceramic material is comparable with that of the lead-based antiferroelectric ceramic material, and the energy storage performance of the NN-based antiferroelectric ceramic material is still poor. One of the strategies to improve the energy storage properties of antiferroelectric ceramic materials is to stabilize the antiferroelectric phase [19]. It is generally believed that the phase stability of ABO 3 type perovskite materials can be regulated by tolerance factors (t values), expressed as:
wherein r A、rB and r O are the ionic radii of the cation at the a-position, the cation at the B-position and the oxygen ion, respectively. Generally, a low value of t is advantageous for stabilizing the antiferroelectric phase, and a high value of t is advantageous for stabilizing the ferroelectric phase [20]. For example, a-site cations having a smaller ionic radius, such as Ca 2+ and Sm 3+, may be added to AN-based antiferroelectric ceramic material to reduce the t-value, thereby improving stability and energy storage properties of the antiferroelectric phase. In addition, the related art has also explored perovskite materials with t values below NN (t=0.967), such as CaZrO 3 (t=0.914) or SrZrO 3 (t=0.947), to form solid solutions with NN with good antiferroelectric phase stability.
Notably, some modified AN-based antiferroelectric ceramic materials and modified NN-based antiferroelectric ceramic materials that have a constant or higher t-value also exhibit enhanced antiferroelectric phase stability, e.g., in Ta-doped AN-based antiferroelectric ceramic material [6] and W-doped AN-based antiferroelectric ceramic material [5], the t-value of which remains constant and increases, respectively. Therefore, the t value is not the only factor affecting the stability of the lead-free antiferroelectric phase, nor is the regulation of the t value always effective.
[1]Luo N,Han K,Zhuo F,Liu L,Chen X,Peng B,et al.Design for high energy storage density and temperature-insensitive lead-free antiferroelectric ceramics.J Mater Chem C.2019;7(17):4999-5008.
[2]Tian Y,Jin L,Zhang H,Xu Z,Wei X,Viola G,et al.Phase transitions in bismuth-modified silver niobate ceramics for high power energy storage.J Mater Chem A.2017;5(33):17525-31.
[3]Gao J,Zhang Y,Zhao L,Lee K-Y,Liu Q,Studer A,et al.Enhanced antiferroelectric phase stability in La-doped AgNbO3:perspectives from the microstructure to energy storage properties.J Mater Chem A.2019;7(5):2225-32.
[4]Luo N,Han K,Zhuo F,Xu C,Zhang G,Liu L,et al.Aliovalent A-site engineered AgNbO3 lead-free antiferroelectric ceramics toward superior energy storage density.J Mater Chem A.2019;7(23):14118-28.
[5]Zhao L,Gao J,Liu Q,Zhang S,Li JF.Silver Niobate Lead-Free Antiferroelectric Ceramics:Enhancing Energy Storage Density by B-Site Doping.ACS Appl Mater Interfaces.2018;10(1):819-26.
[6]Zhao L,Liu Q,Gao J,Zhang S,Li JF.Lead-Free Antiferroelectric Silver Niobate Tantalate with High Energy Storage Performance.Adv Mater.2017;29(31):1701824.
[7]Xu C,Fu Z,Liu Z,Wang L,Yan S,Chen X,et al.La/Mn Codoped AgNbO3Lead-Free Antiferroelectric Ceramics with Large Energy Density and Power Density.ACS Sustainable Chem Eng.2018;6(12):16151-9.
[8]Han K,Luo N,Jing Y,Wang X,Peng B,Liu L,et al.Structure and energy storage performance of Ba-modified AgNbO3 lead-free antiferroelectric ceramics.Ceram Int.2019;45(5):5559-65.
[9]Ren P,Ren D,Sun L,Yan F,Yang S,Zhao G.Grain size tailoring and enhanced energy storage properties of two-step sintered Nd3+-doped AgNbO3.J Eur Ceram Soc.2020;40(13):4495-502.
[10]Luo N,Han K,Cabral MJ,Liao X,Zhang S,Liao C,et al.Constructing phase boundary in AgNbO3 antiferroelectrics:pathway simultaneously achieving high energy density and efficiency.Nat Commun.2020;11(1):4824.
[11]Lu Z,Bao W,Wang G,Sun S-K,Li L,Li J,et al.Mechanism of enhanced energy storage density in AgNbO3-based lead-free antiferroelectrics.Nano Energy.2021;79:105423.
[12]Zhao L,Liu Q,Zhang SJ,Li JF.Lead-free AgNbO3 anti-ferroelectric ceramics with an enhanced energy storage performance using MnO2modification.J Mater Chem C.2016;4(36):8380-4.
[13]Zhang M-H,Hadaeghi N,Egert S,Ding H,Zhang H,Groszewicz PB,et al.Design of Lead-Free Antiferroelectric(1–x)NaNbO3–xSrSnO3 Compositions Guided by First-Principles Calculations.Chem Mater.2020;33(1):266-74.
[14]Xie A,Fu J,Zuo R.Achieving stable relaxor antiferroelectric P phase in NaNbO3-based lead-free ceramics for energy-storage applications.Journal of Materiomics.2022;8(3):618-26.
[15]Qi H,Xie A,Fu J,Zuo R.Emerging Antiferroelectric Phases with Fascinating Dielectric,Polarization and Strain Response in NaNbO3-(Bi0.5Na0.5)TiO3 Lead-Free Binary System.Acta Mater.2021;208:116710.
[16]Qi H,Zuo R,Xie A,Fu J,Zhang D.Excellent energy-storage properties of NaNbO3-based lead-free antiferroelectric orthorhombic P-phase(Pbma)ceramics with repeatable double polarization-field loops.J Eur Ceram Soc.2019;39(13):3703-9.
[17]L,Zhang M-H,Fu Y,Koruza J,/>J.NaNbO3-based antiferroelectric multilayer ceramic capacitors for energy storage applications.J Eur Ceram Soc.2021;41(11):5519-25.
[18]Zhang L,Pu Y,Chen M,Shi Y,Shang J,Yang Y,et al.Novel(1-x)NaNbO3-xBi2/3HfO3based,lead-free compositions with stable antiferroelectric phase and high energy density and switching field.Chem Eng J.2023;457:141376.
[19]Yang L,Kong X,Li F,Hao H,Cheng Z,Liu H,et al.Perovskite lead-free dielectrics for energy storage applications.Prog Mater Sci.2019;102:72-108.
[20]Hao X,Zhai J,Kong LB,Xu Z.Acomprehensive review on the progress of lead zirconate-based antiferroelectric materials.Prog Mater Sci.2014;63:1-57.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems: the research in the related art mainly focuses on improving the stability of the antiferroelectric phase by regulating and controlling the t value, so that the energy storage performance of the antiferroelectric ceramic material is improved, but the t value regulation and control is not always effective, so that the research is insufficient, and the energy storage performance of the antiferroelectric ceramic material is still to be further improved; in addition, the influence of the stability of the field-induced ferroelectric phase on the energy storage performance of the lead-free antiferroelectric ceramic material is not researched in the related art, so the embodiment of the invention provides a sodium niobate-based antiferroelectric ceramic material, a preparation method thereof and a capacitor.
The present invention aims to solve at least one of the technical problems in the related art to some extent. For this purpose, the embodiment of the invention provides a sodium niobate-based antiferroelectric ceramic material, a preparation method thereof and a capacitor. The ceramic material stabilizes the antiferroelectric phase by reducing the polarizability of B-site cations, thereby improving the energy storage performance of the ceramic material, and further, the stability of the field-induced ferroelectric phase can be broken by introducing aliovalent ions La 3+ and vacancies into the preferable components, and the energy storage performance of the ceramic material is further improved.
The embodiment of the invention provides a sodium niobate-based antiferroelectric ceramic material, which has the chemical formula:
(Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, where x=4% -10%;
or (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, where y=0.5% -2%;
or (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, where y=0.5% -2%).
The ceramic material of the embodiment of the invention has the following advantages and technical effects:
(1) In the Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3 ceramic of the embodiment of the invention (Sn is used as 4+ Substitution of Nb 5+/>, in NaNbO 3 The average polarizability of B-site cations is reduced, so that the displacement of the B-site cations is reduced, the inclination of the BO 6 octahedron is weakened, the antiferroelectric stability is enhanced, a double-hysteresis loop is realized, and the energy storage performance of the ceramic material is further improved;
(2) The Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 ceramic and the Na 0.94- yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3 ceramic of the embodiment of the invention are replaced by La 3+ (Na + in Na 0.94K0.03Bi0.03)(Nb0.94Sn0.06)O3 is introduced with aliovalent ion La 3+, and simultaneously, a vacancy is introduced at Na + or Nb 5+, thereby breaking the stability of a field-induced ferroelectric phase and further improving the energy storage performance of the ceramic material;
(3) The ceramic material of the embodiment of the invention has the characteristic antiferroelectric-ferroelectric phase change of antiferroelectric materials, can still keep a higher capacitance value under high direct current bias, and has excellent energy storage performance; meanwhile, as the band gap of the sodium niobate is wider and the temperature stability of the ceramic material is better, the ceramic material of the embodiment of the invention is expected to be used in high-temperature and high-direct-current bias application scenes, such as inverter modules of electric automobiles.
Preferably, in some embodiments, the ceramic material has the formula: (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, where x=6% -8%.
More preferably, in some embodiments, the ceramic material has the formula: (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, x=6%.
Preferably, in some embodiments, the ceramic material has the formula: (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, where y=0.5% -1.0%).
More preferably, in some embodiments, the ceramic material has the formula: (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, where y=0.5%.
Preferably, in some embodiments, the ceramic material has the formula: (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, where y=0.5% -1.0%).
More preferably, in some embodiments, the ceramic material has the formula: (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, where y=0.5%.
The embodiment of the invention also provides a preparation method of the sodium niobate-based antiferroelectric ceramic material, which comprises the following steps:
(1) When the chemical formula of the ceramic material is (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, na 2CO3、K2CO3、Bi2O3、Nb2O5 and SnO 2 are used as raw materials, when the chemical formula of the ceramic material is (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 or (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, Na2CO3、K2CO3、Bi2O3、Nb2O5、SnO2 and La 2O3 are used as raw materials, the raw materials are mixed according to the stoichiometric ratio of the ceramic material to obtain a raw material mixture, and then the raw material mixture is subjected to ball milling treatment for the first time to obtain raw material mixed powder;
(2) Calcining the raw material mixed powder to obtain ceramic powder;
(3) Performing secondary ball milling treatment on the ceramic powder, and then pressing the ceramic powder into ceramic sheets;
(4) Performing cold isostatic pressing treatment on the ceramic sheet to obtain a ceramic blank;
(5) And sintering the ceramic blank to obtain the ceramic material.
Preferably, in some embodiments, in step (2), the temperature of the calcination treatment is 880-920 ℃; and/or the calcination treatment is carried out for 3-5 hours.
Preferably, in some embodiments, in step (3), the time of the secondary ball milling treatment is 20h to 28h; and/or the ceramic particles have a diameter of 8mm to 12mm.
Preferably, in some embodiments, in step (4), the cold isostatic pressure treatment is at a pressure of 200MPa to 300MPa.
Preferably, in step (5), the sintering process is performed at a temperature of 1050 ℃ to 1200 ℃ when the ceramic material has a chemical formula (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3), and 1270 ℃ to 1300 ℃ when the ceramic material has a chemical formula (Na 0.94- 3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 or (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3).
The preparation method of the ceramic material provided by the embodiment of the invention has the following advantages and technical effects:
compared with other synthesis methods such as a sol-gel method, a hydrothermal method and the like, the preparation method provided by the embodiment of the invention has the advantages of low raw material cost, high yield and simple process.
The embodiment of the invention also provides a capacitor, and the dielectric material of the capacitor is the ceramic material of the embodiment of the invention or the ceramic material prepared by the preparation method of the embodiment of the invention.
The capacitor provided by the embodiment of the invention has the following advantages and technical effects:
The capacitor provided by the embodiment of the invention has excellent energy storage performance and better temperature stability, so that the capacitor provided by the embodiment of the invention is expected to be used in high-temperature and high-direct-current bias application scenes, such as an inverter module of an electric automobile.
Drawings
FIG. 1 shows the dielectric constant (. Epsilon. r) and dielectric loss (. Tan. Delta.) of the ceramic materials of examples 1 to 4 at a frequency of 1kHz as a function of temperature; wherein, (a) is a graph of dielectric constant (epsilon r) as a function of temperature; (b) is a graph of dielectric loss (tan delta) as a function of temperature;
FIG. 2 shows XRD refinement of the ceramic materials of examples 1-4; wherein, (a) is the XRD refinement of example 1; (b) is the XRD refinement of example 2; (c) is the XRD refinement of example 3; (d) is the XRD refinement of example 4; the spatial group symbols of the P phase, the Q phase and the R phase are Pbcm, P2 1 ma and Pbnm respectively, and the impurity phase SnO 2 is marked by an asterisk in the step (d);
FIG. 3 shows SEM pictures of the ceramic materials of examples 1-4; wherein, (a) is an SEM photograph of example 1; (b) is an SEM photograph of example 2; (c) is an SEM photograph of example 3; (d) is an SEM photograph of example 4; (d) The white point in (3) is impurity phase SnO 2.
FIG. 4 shows the energy storage properties of the ceramic materials of examples 1-4; wherein, (a) is the maximum polarization intensity (P max) of the ceramic material of examples 1-4 under an applied electric field; (b) Hysteresis loops (P-E) at 250kV/cm for the ceramic materials of examples 1-4; (c) A current density-electric field strength (J-E) curve at 250kV/cm for the ceramic materials of examples 1-4; (d) E AF、EFA and delta E are the changes of KBS concentration;
FIG. 5 shows the hysteresis loops (P-E) measured for the ceramic materials of examples 1-4 at different frequencies and different temperatures; wherein, (a) is in the frequency range of 0.1-100 Hz; (b) in the temperature range of 30-150 ℃;
FIG. 6 shows a schematic representation of the calculation of the energy storage density by means of the hysteresis loop (P-E); wherein the shadow areas are the dischargeable energy density (W rec) and the lost energy density (W loss), respectively; the energy efficiency (η) may be calculated from the formula in the figure; the phase transition electric fields E AF and E FA can be derived from the current-electric field strength curve (I-E);
The raman spectra of the ceramic materials of examples 1-4 are shown in fig. 7 (a); (b) Shows the variation of v 1 band peak position with KBS concentration;
The XRD patterns of the ceramic materials of example 2 and examples 5-12 are shown in FIG. 8 (a); wherein, the triangle symbol and the square symbol respectively mark impurity phases SnO 2 and K 3NbO4; (b) The relative permittivity (. Epsilon. r) of the ceramic materials of examples 5-8 is shown as a function of temperature at 1 kHz; (c) The relative permittivity (. Epsilon. r) of the ceramic materials of examples 9-12 at 1kHz is shown as a function of temperature;
FIG. 9 shows SEM pictures of ceramic materials of examples 5-8; wherein, (a) is an SEM photograph of example 5; (b) is an SEM photograph of example 6; (c) is an SEM photograph of example 7; (d) is an SEM photograph of example 8;
FIG. 10 shows SEM pictures of ceramic materials of examples 9-12; wherein, (a) is an SEM photograph of example 9; (b) is an SEM photograph of example 10; (c) is an SEM photograph of example 11; (d) is an SEM photograph of example 12;
FIG. 11 shows the hysteresis loops (P-E) at 250kV/cm for the ceramic materials of example 2 and examples 5-12; wherein (a) is the hysteresis loop (P-E) of the ceramic materials of examples 2 and examples 5-6 at 250 kV/cm; (b) Hysteresis loops (P-E) at 250kV/cm for the ceramic materials of examples 7-8; (c) A hysteresis loop (P-E) at 250kV/cm for the ceramic materials of example 2 and examples 9-10; (d) Hysteresis loops (P-E) at 250kV/cm for the ceramic materials of examples 11-12;
The unipolar hysteresis loops (P-E) of the ceramic materials of examples 2 and examples 5-6, examples 9-10 are shown in fig. 12 (a). (b) Current density-electric field strength (J-E) curves for the ceramic materials of examples 2 and examples 5-6, examples 9-10 are shown; (c) The maximum polarization intensity P max and the remnant polarization intensity P r of the ceramic materials of examples 2 and examples 5-6, examples 9-10 are shown;
FIG. 13 shows a graph of the cyclic stability test of the ceramic material of example 9; wherein (a) shows the unipolar hysteresis loop of the ceramic material of example 9 under different electric fields; (b) Showing the releasable energy density (W rec) and energy efficiency (η) of the ceramic material of example 9 under an applied electric field; (c) A comparison of the energy storage properties between the ceramic material of example 9 and the AN-based antiferroelectric ceramic material [1-4,5,6,7-12] and the NN-based antiferroelectric ceramic material [13,14,15,16-18] in the related art is shown; (d) Shows the monopolar hysteresis loop (P-E) of the ceramic material of example 9 measured at 400kV/cm and a temperature range of 30-180deg.C; (e) A graph showing the releasable energy density (W rec) and energy efficiency (η) as a function of temperature at 400kV/cm for the ceramic material of example 9; (f) Shows the monopolar hysteresis loop (P-E) measured at 400kV/cm and after various cycles up to 105 for the ceramic material of example 9; (g) A graph showing the releasable energy density (W rec) and energy efficiency (η) as a function of the number of cycles at 400kV/cm for the ceramic material of example 9;
FIG. 14 (a) shows the Weibull plots for the ceramic materials of examples 2 and examples 5-6, examples 9-10; (b) The weibull characteristic breakdown strength (Eb) and weibull modulus (m) of the ceramic materials of examples 2 and examples 5-6, examples 9-10 are shown.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
First aspect
The embodiment of the invention provides a sodium niobate-based antiferroelectric ceramic material, which has the chemical formula: (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, where x=4% -10%, e.g. 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.
The ceramic material of the embodiment of the invention is (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, the chemical formula can also be written as (1-x) NaNbO 3-x(K0.5Bi0.5)SnO3 in the embodiment of the invention (Sn in the Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3 ceramic) 4+ Replaces Nb 5+/>, in NaNbO 3 And the average polarizability of B-site cations is reduced, so that the displacement of the B-site cations is reduced, and the BO 6 octahedron is inclined, so that the antiferroelectric stability is enhanced, double electric hysteresis loops are realized, and the energy storage performance of the ceramic material is improved.
Preferably, in some embodiments, the ceramic material has the formula: more preferably, in some embodiments, the ceramic material has the formula (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, wherein x=6% >) when x is too small, it is detrimental to decrease the residual polarization of the ceramic material, P r, to increase the stability of the antiferroelectric phase, and thus the energy storage performance of the ceramic material.
The embodiment of the invention also provides a preparation method of the sodium niobate-based antiferroelectric ceramic material, which comprises the following steps:
(1) Taking Na 2CO3、K2CO3、Bi2O3、Nb2O5 and SnO 2 as raw materials, mixing according to the stoichiometric ratio of the ceramic material to obtain a raw material mixture, and performing ball milling on the raw material mixture for one time to obtain raw material mixed powder;
(2) Calcining the raw material mixed powder to obtain ceramic powder;
(3) Performing secondary ball milling treatment on the ceramic powder, and then pressing the ceramic powder into ceramic sheets;
(4) Performing cold isostatic pressing treatment on the ceramic sheet to obtain a ceramic blank;
(5) And sintering the ceramic blank to obtain the ceramic material.
The preparation method of the embodiment of the invention adopts a solid phase method to synthesize the ceramic material of the embodiment of the invention, and other synthesis methods such as a sol-gel method, a hydrothermal method and the like can also synthesize the ceramic material of the embodiment of the invention, but the preparation method has the problems of high raw material cost, low yield, complex process and the like.
Preferably, in some embodiments, in step (1), the ingredients are prepared after drying the various raw materials in advance, for example, drying at 100-150 ℃ for 12-24 hours, so as to facilitate accurate preparation and reduce errors.
Preferably, in some embodiments, the medium balls subjected to the ball milling treatment in the step (1) may be one or more of yttrium stabilized zirconia balls, agate balls, nylon balls and the like, so as to facilitate uniform grinding. More preferably, in some embodiments, the ball to material ratio is 1 (5-10), e.g., the ball to material ratio may be 1:5, 1:6, 1:7, 1:9, 1:10, etc.
Preferably, in some embodiments, the step (1) of ball milling is performed after mixing the raw material mixture with ethanol, so as to facilitate uniform grinding. More preferably, in some embodiments, the amount of ethanol added is 60% -120% of the mass of the feedstock mixture, such as 60%, 75%, 90%, 100%, 120%, etc.
Preferably, in some embodiments, the time of one ball milling treatment in step (1) is 10h-16h, e.g., 10h, 11h, 12h, 13h, 14h, 15h, 16h, etc. When the ball milling time is too short, the particle size of the obtained raw material mixed powder is too large, which is not beneficial to shortening the time of subsequent calcination treatment and reducing the cost and enhancing the efficiency. When the ball milling time is too long, the improvement effect on the subsequent calcination treatment is not great, but the cost reduction and the synergy are not facilitated.
Preferably, in some embodiments, after the primary ball milling treatment in the step (1), a screen with more than 60 meshes is adopted for screening to obtain raw material mixed powder, so that particles with overlarge particle size are conveniently screened out, and raw material mixed powder with smaller particle size is obtained, further, the time of the subsequent primary calcination treatment is conveniently shortened, and the cost reduction and the efficiency improvement are facilitated.
Preferably, in some embodiments, the temperature of the calcination treatment in step (2) is 880-920 ℃, e.g., 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, etc.; and/or the calcination treatment is for a period of time ranging from 3h to 5h, such as 3h, 3.5h, 4h, 4.5h, 5h, etc. The calcination treatment serves to form the starting material into the desired product. If the temperature of the calcination treatment is too low or the time is too short, the subsequent sintering of the ceramic is not favored. If the temperature of the calcination treatment is too high or too long, volatilization of Na and Bi elements can be caused, which is unfavorable for densification of the subsequent ceramics.
Preferably, in some embodiments, the medium balls subjected to the secondary ball milling treatment in the step (3) may be one or more of yttrium stabilized zirconia balls, agate balls, nylon balls and the like, so as to facilitate uniform grinding. More preferably, in some embodiments, the ball to material ratio is 1 (5-10), e.g., the ball to material ratio may be 1:5, 1:6, 1:7, 1:9, 1:10, etc.
Preferably, in some embodiments, the ceramic powder and MnO 2 are mixed in step (3) and then subjected to a secondary ball milling process. The purpose of adding MnO 2 is to reduce leakage current and further improve the energy storage performance of the subsequently formed ceramic material. More preferably, in some embodiments, mnO 2 is added in an amount of 0.1% -1% by mass of ceramic powder, e.g., 0.1%, 0.3%, 0.5%, 0.7%, 1%, etc.
Preferably, in some embodiments, the secondary ball milling treatment in step (3) is performed after mixing the ceramic powder with ethanol, so as to facilitate uniform grinding. More preferably, in some embodiments, the ethanol is added in an amount of 60% -120% of the ceramic powder mass, such as 60%, 75%, 90%, 100%, 120%, etc.
Preferably, in some embodiments, the time of the secondary ball milling treatment in step (3) is 20h-28h, e.g., 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, etc. When the ball milling time is too short, the particle size of the obtained ceramic powder is too large, which is not beneficial to reducing holes in the ceramic sheet pressed subsequently. When the ball milling time is too long, the improvement effect on the pressing effect of the subsequent ceramic plate is not great, the ball milling balls are easy to wear, impurities are introduced, and the cost reduction and the synergy are not facilitated.
Preferably, in some embodiments, screening is performed by adopting a screen with more than 100 meshes after the secondary ball milling treatment in the step (3), so as to conveniently screen out particles with oversized particle size, obtain powder with smaller particle size, and further facilitate subsequent pressing into uniform ceramic sheets.
Preferably, in some embodiments, when the ceramic sheet is circular in step (3), the diameter of the ceramic sheet is 8mm-12mm, e.g., 8mm, 9mm, 10mm, 11mm, 12mm, etc. When the diameter of the ceramic plate is too small, the ceramic shrinkage in the subsequent sintering treatment is too large, which is unfavorable for subsequent processing and testing. When the diameter of the ceramic plate is too large, the subsequent ceramic plate is not favorable for full and uniform sintering.
Preferably, in some embodiments, the pressure of the cold isostatic pressing treatment in step (4) is 200MPa-300MPa, e.g. 200MPa, 210MPa, 220MPa, 230MPa, 240MPa, 250MPa, 260MPa, 270MPa, 280MPa, 290MPa, 300MPa, etc. The cold isostatic pressing treatment has the effect of improving the compactness of the ceramic. When the pressure is too small, the ceramic density is not improved. When the pressure is too large, the ceramic density is not obviously improved, and the phenomenon of die breakage is easy to occur. Since the cold isostatic pressing is performed by pressing the ceramic simultaneously from all directions, it is necessary to press the ceramic into a cake shape by uniaxial pressing before cold isostatic pressing. If cold isostatic pressing is directly performed, the shape of the ceramic is difficult to control.
Preferably, in some embodiments, the temperature of the sintering process in step (5) is 1050 ℃ -1200 ℃, e.g., 1050 ℃, 1080 ℃, 1100 ℃, 1120 ℃, 1150 ℃, 1180 ℃, 1200 ℃, etc. The sintering process serves to densify the ceramic. When the sintering temperature is too low, the material is not favorable for full diffusion, and further the ceramic density is not favorable for improvement. When the sintering temperature is too high, volatilization of Na and Bi elements is easy to cause, so that holes in the ceramic are increased, and the compactness is not improved.
Second aspect
The embodiment of the invention also provides a sodium niobate-based antiferroelectric ceramic material, which has the chemical formula: (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 where y=0.5% -2%, or (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3 where y=0.5% -2%).
(Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 ceramic can be regarded as being substituted with y La 3+ (Na + in Na 0.94K0.03Bi0.03)(Nb0.94Sn0.06)O3 ceramic, due to the different valence states of Na + and La 3+, while generating 2y Na vacancies at the Na position.) A (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3 ceramic can be regarded as being substituted with y La 3+ (Na + in Na 0.94K0.03Bi0.03)(Nb0.94Sn0.06)O3 ceramic, due to the different valence states of Na + and La 3+, while generating 0.4y Nb vacancies at the Nb position).
Because the valence difference between La 3+ and Na + is 2, doping La 3+ in place of Na + requires cation vacancies to maintain electroneutrality. One method is to create Na vacancies with one negative charge, and the other method is to create Nb vacancies with 5 negative charges. Because the two vacancies are charged in different amounts, the concentration required to maintain electroneutrality is also different.
Although (Na 0.94K0.03Bi0.03)(Nb0.94Sn0.06)O3 ceramic has stable antiferroelectric phase and related characteristic double-electric hysteresis loop, the stability of the field-induced ferroelectric phase is still remarkable, and the energy storage performance is still further improved, the ceramic materials of the embodiment of the invention (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 and Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3 contain aliovalent ions La 3+, and simultaneously, vacancies are introduced at Na + or Nb 5+, so that the stability of the field-induced ferroelectric phase can be broken, and the energy storage performance of the ceramic materials is further improved.
Compared with (Na 0.94K0.03Bi0.03)(Nb0.94Sn0.06)O3 ceramic, (Na 0.94-yLayK0.03Bi0.03)(Nb0.94- 0.4ySn0.06)O3 ceramic has enhanced phase transition electric field), which shows that the stability of the ferroelectric phase of the field is reduced, and the stability of the antiferroelectric phase is improved, and the energy storage performance of the ceramic is improved.
XRD detection shows that the ceramic has A-site vacancies (the Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 ceramic has impurity phases SnO 2 and K 3NbO4, while the Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3 ceramic has B-site vacancies (the Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3 ceramic has no obvious impurity phase, and the Na 0.94- 3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 ceramic has higher energy storage performance, so that the ceramic with B-site vacancies is preferable).
Preferably, in some embodiments, the ceramic material has the formula: (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, where y=0.5% -1%) when the y value is too large, the relaxation ferroelectricity of the ceramic is enhanced, masking the antiferroelectricity.
More preferably, in some embodiments, the ceramic material has the formula: (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, where y=0.5%. Y=0.5% (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 ceramic has the highest phase transition electric field and the lowest remnant polarization P r, and therefore the overall energy storage performance is best, higher than the other (Na 0.94- 3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 ceramic).
Preferably, in some embodiments, the ceramic material has the formula: (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, where y=0.5% -1%) when the y value is too large, the relaxation ferroelectricity of the ceramic is enhanced, masking the antiferroelectricity.
More preferably, in some embodiments, the ceramic material has the formula: (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, where y=0.5%. Y=0.5% (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3 ceramic has the highest phase transition electric field and the lowest remnant polarization P r, and therefore the overall energy storage performance is best, higher than the other (Na 0.94- yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3 ceramic).
The embodiment of the invention also provides a preparation method of the sodium niobate-based antiferroelectric ceramic material, which comprises the following steps:
(1) Mixing Na2CO3、K2CO3、Bi2O3、Nb2O5、SnO2 and La 2O3 serving as raw materials according to the stoichiometric ratio of the ceramic material to obtain a raw material mixture, and performing ball milling treatment once to obtain raw material mixed powder;
(2) Calcining the raw material mixed powder to obtain ceramic powder;
(3) Performing secondary ball milling treatment on the ceramic powder, and then pressing the ceramic powder into ceramic sheets;
(4) Performing cold isostatic pressing treatment on the ceramic sheet to obtain a ceramic blank;
(5) And sintering the ceramic blank to obtain the ceramic material.
Preferably, in some embodiments, the temperature of the sintering process of step (5) is 1270 ℃ to 1300 ℃. Such as 1270 ℃, 1280 ℃, 1290 ℃, 1300 ℃, etc. The sintering process serves to densify the ceramic. When the sintering temperature is too low, the material is not favorable for full diffusion, and further the ceramic density is not favorable for improvement. When the sintering temperature is too high, volatilization of Na and Bi elements is easy to cause, so that holes in the ceramic are increased, and the ceramic density is not improved. In addition, reference is made to the preparation method of the first aspect for other preferred procedures.
Third aspect of the invention
The embodiment of the invention also provides a capacitor, and the dielectric material of the capacitor is the ceramic material of the embodiment of the invention or the ceramic material prepared by the preparation method of the embodiment of the invention.
The capacitor provided by the embodiment of the invention has excellent energy storage performance and better temperature stability, so that the capacitor provided by the embodiment of the invention is expected to be used in high-temperature and high-direct-current bias application scenes, such as an inverter module of an electric automobile. The present invention will be described in detail with reference to the following examples and drawings.
Example 1
A sodium niobate-based antiferroelectric ceramic material having the chemical formula (Na 1-xK0.5xBi0.5x)(Nb1- xSnx)O3, where x=4%, and designated NN-4 KBS).
The preparation method of the sodium niobate-based antiferroelectric ceramic material comprises the following steps:
(1) Baking high-purity Na2CO3(99.95％-100.05％,Alfa Aesar)、K2CO3(99.99％,Aladdin)、Bi2O3(99.99％,Alfa Aesar)、Nb2O5(99.99％,Aladdin) and SnO 2 (99.9% Aladin) serving as raw materials at 120 ℃ overnight and mixing according to the stoichiometric ratio of a sodium niobate-based ceramic material to obtain a raw material mixture, putting the raw material mixture into a ball milling tank, adding ethanol with the same mass as the raw material mixture and yttrium-stabilized zirconia balls with the ball material ratio of 1:5, performing ball milling for one time to obtain slurry after ball milling for 12 hours, separating the slurry from the yttrium-stabilized zirconia balls, drying the slurry, and sieving the slurry with a 60-mesh sieve to obtain raw material mixed powder:
(2) Placing the raw material mixed powder into an alumina crucible, calcining in a muffle furnace at a constant temperature of 900 ℃ for 4 hours to obtain ceramic powder;
(3) Placing ceramic powder into a ball milling tank, adding MnO 2 with the mass of 0.5% of the ceramic powder and yttrium stabilized zirconia balls with the mass of ethanol and ball material ratio of 1:5 to the ceramic powder, performing secondary ball milling treatment, performing ball milling for 24 hours to obtain slurry, drying the slurry, sieving with a 100-mesh screen, and pressing into a round ceramic sheet with the diameter of 10mm under the uniaxial pressure of 30 MPa;
(4) Performing cold isostatic pressing treatment on the ceramic sheet under 220MPa to obtain a ceramic blank;
(5) And (3) placing the ceramic blank into an alumina crucible, sintering in a muffle furnace at a constant temperature of 1050 ℃ for 24 hours, and obtaining the ceramic material.
Example 2
The sodium niobate-based antiferroelectric ceramic material of this example has a chemical formula (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, where x=6%, which can also be written as (1-x) NaNbO 3-x(K0.5Bi0.5)SnO3. This ceramic material is denoted NN-6KBS.
Example 3
The sodium niobate-based antiferroelectric ceramic material of this example has a chemical formula (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, where x=8%, which can also be written as (1-x) NaNbO 3-x(K0.5Bi0.5)SnO3. This ceramic material is denoted NN-8KBS.
Example 4
The sodium niobate-based antiferroelectric ceramic material of this example has a chemical formula (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, where x=10%, which can also be written as (1-x) NaNbO 3-x(K0.5Bi0.5)SnO3. This ceramic material is denoted NN-10KBS.
Example 5
A sodium niobate-based antiferroelectric ceramic material having the chemical formula (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, where y=0.5%; this ceramic material is designated 0.5 La-VA).
The preparation method of this example is different from that of example 1 in that La 2O3 (99.99%, aladin) is added in the stoichiometric ratio in step (1); the sintering treatment temperature in the step (5) is 1280 ℃.
Example 6
The sodium niobate-based antiferroelectric ceramic material of this example has a chemical formula (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, where y=1.0%. This ceramic material is denoted as 1.0La-VA., otherwise identical to example 5.
Example 7
The sodium niobate-based antiferroelectric ceramic material of this example has a chemical formula (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, where y=1.5%. This ceramic material is denoted as 1.5La-VA. otherwise identical to example 5.
Example 8
The sodium niobate-based antiferroelectric ceramic material of this example has a chemical formula (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, where y=2.0%. This ceramic material is denoted as 2.0La-VA., otherwise identical to example 5.
Example 9
A sodium niobate-based antiferroelectric ceramic material having the chemical formula (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, where y=0.5%; this ceramic material is designated 0.5 La-VB).
The preparation method of this example is different from that of example 1 in that La 2O3 (99.99%, aladin) is added in the stoichiometric ratio in step (1); the sintering treatment temperature in the step (5) is 1270 ℃.
Example 10
The sodium niobate-based antiferroelectric ceramic material of this example has a chemical formula (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, where y=1.0%. This ceramic material is denoted as 1.0La-VB., otherwise identical to example 9.
Example 11
The sodium niobate-based antiferroelectric ceramic material of this example has a chemical formula (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, where y=1.5%. This ceramic material is denoted as 1.5La-VB. otherwise identical to example 9.
Example 12
The sodium niobate-based antiferroelectric ceramic material of this example has a chemical formula (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, where y=2.0%, and this ceramic material is denoted as 2.0La-VB., with the other conditions being the same as in example 9.
Performance test:
The crystal structure of the powder obtained after grinding the ceramic material was studied using an X-ray diffractometer (D8 Advanced, bruker). Microstructure and elemental analysis field emission scanning electron microscopy (FE-SEM) (Merlin compactZeiss) with properties is equipped with an energy dispersive X-ray (EDS) detector (Ultim Max, oxford Instruments). The ceramic material was annealed at 150 ℃ below the corresponding sintering temperature for 15 minutes prior to scanning electron microscopy for good polishing and hot etching. A Raman spectrum of the annealed ceramic material was recorded by a Raman imaging microscope (Alpha 300R, WITec) using a 532nm laser as an excitation light source.
The ceramic material is thinned and electrodes are deposited prior to electrical characterization. For dielectric measurements, the ceramic material is thinned to about 200 μm. Silver paste (dupont 7723) was applied to both sides of the ceramic material by screen printing and baked at 550 c for 30 minutes to form electrodes. Dielectric properties at different temperatures were measured with an impedance analyzer (E4990A, keysight) and a temperature controller (HFSE 91-PB2, linkam). For polarized electric field (P-E) hysteresis loop measurement, the ceramic material was thinned and polished to about 50 μm, and a gold electrode of 1mm diameter was deposited by sputtering. Hysteresis loops (P-E) at 1Hz and different temperatures were measured with a ferroelectric tester (aixACCT TF1000,1000).
The results of performance testing of the sodium niobate-based antiferroelectric ceramic materials of examples 1 to 12 are shown in fig. 1 to 14. The recoverable energy density W rec and the energy efficiency eta calculated from the hysteresis loop (P-E) are shown in Table 1.
TABLE 1 recoverable energy Density W rec and energy efficiency eta for the ceramic materials of examples 1-12
The performance test results were specifically analyzed as follows:
First aspect
Fig. 1 shows the variation of the dielectric constant (epsilon r) and dielectric loss (tan delta) with temperature at a frequency of 1kHz for each ceramic material. The dielectric peak of NN-4KBS at about 300℃in FIG. 1 (a) corresponds to the phase transition between the antiferroelectric P-phase and the antiferroelectric R-phase, which peak is at about 360℃in pure NaNbO 3. As the KBS doping level increases from 4% to 8%, the corresponding temperature of the dielectric peak decreases. When the KBS concentration reaches 10%, the dielectric peak suddenly shifts to-90 ℃ and widens, which shows that the NN-KBS system belongs to a second NN-ABO 3 -based relaxor ferroelectric, and is characterized in that when the doping concentration of ABO 3 reaches a critical concentration, the dielectric peak suddenly shifts to low temperature and the relaxation characteristic occurs. The increase in dielectric loss of each ceramic material at high temperatures is due to the increase in ionic conductivity.
The research of the embodiment of the invention shows that the antiferroelectric phase is kept unchanged as long as the KBS concentration is lower than the critical concentration, and the dielectric peak mutation occurs when the KBS concentration exceeds the critical concentration. Thus, it is expected that the phase structure of NN-4KBS, NN-6KBS and NN-8KBS ceramics will include the antiferroelectric P phase (space group Pbcm). Considering that the ferroelectric Q phase (space group P2 1 ma) generally coexists with the P phase due to the small energy difference between the two phases, the XRD patterns of the respective ceramic materials are refined using the P phase and Q phase as models. Since the phase transition peak of NN-8KBS is below room temperature, as shown in fig. 1 (a), another antiferroelectric R phase (space group Pbnm) is also included in the refinement process of the ceramic material. The results of the refinement of NN-100xKBS ceramic are shown in FIG. 2. The results show that as the KBS concentration increases, the P phase content increases, and the P phase content in NN-8KBS reaches 100%, which shows that the addition of KBS with lower B-site polarization is beneficial to the formation of an antiferroelectric phase. When the KBS concentration was increased to 10%, an impurity phase SnO 2 appeared, as indicated by an asterisk in FIG. 2 (d). Impurity phases can also be observed in SEM images, as shown in fig. 3 (d). The appearance of SnO 2 impurity phases observed in NN-10KBS solid solutions may be related to the limited solubility of Sn-containing perovskites in NN.
The present examples measured the bipolar hysteresis loop (P-E) of NN-100xKBS ceramics at different fields until breakdown occurred. The breakdown strength of all four ceramic materials was around 300kV/cm, which is related to their dense microstructure, as shown in fig. 3. The maximum polarization (P max) as the applied electric field is shown in FIG. 4 (a). When x <10%, P max of the ceramic material transitions at the critical electric field, which corresponds to a field induced antiferroelectric-ferroelectric phase transition. The critical electric field increases with increasing KBS concentration, indicating that the addition of KBS improves the stability of the antiferroelectric phase. Notably, the P max variation of NN-10KBS is quite stable, which is related to its relaxation properties. The hysteresis loop (P-E) of NN-100xKBS ceramic at 250kV/cm is compared in FIG. 4 (b). Ceramic materials containing x=4% -8% exhibit double hysteresis loops of antiferroelectric character. NN-4KBS and NN-6KBS exhibit comparable values of P max, which have lower remnant polarization (P r), indicating that more of the ferroelectric Q phase returns to the antiferroelectric P phase after removal of the electric field, indicating that the antiferroelectric phase has higher stability. Although NN-8KBS showed lower P r, its P max was significantly lower than NN-6KBS, probably due to the comparison with Nb 5+ In comparison, sn 4+/>Lower polarizability of the light source. Accordingly, embodiments of the present invention preferably use NN-6KBS ceramics whose hysteresis loops (P-E) are measured at different frequencies and temperatures, as shown in FIG. 5. These ferroelectric hysteresis loops (P-E) retain antiferroelectric properties, indicating that the double ferroelectric hysteresis loops do result from antiferroelectric effects, not from artifacts such as defective dipoles. Antiferroelectric/ferroelectric phase stability can also be characterized by a phase transition electric field E AF (the critical electric field for antiferroelectric to ferroelectric phase transition) and E FA (the electric field for ferroelectric return to antiferroelectric phase), which represent the threshold electric fields for antiferroelectric-ferroelectric phase transition, respectively. The threshold electric field may be obtained from a current density-electric field strength (J-E) curve, as shown in fig. 6. In the positive field region, positive and negative current density peaks are associated with E AF and E FA, respectively. NN-10KBS exhibited two current density peaks instead of four, indicating that it changed to a relaxor ferroelectric. Although another antiferroelectric R phase appears in NN-10KBS, no double hysteresis loop is reported for NN-based ceramics with R phase. The E AF、EFA and Δe (E AF-EFA) values of the ceramic materials with x=4% -8% are compared in fig. 4 (d). As KBS concentration increases, the current density value increases, indicating that a larger electric field is required to trigger the antiferroelectric-ferroelectric phase transition, thereby improving antiferroelectric phase stability. It can be seen that NN-6KBS ceramic has the smallest E AF-EFA difference and P max is higher, so NN-6KBS is preferred for subsequent investigation.
To fully understand the root cause of KBS in NN-100xKBS ceramic to increase NN antiferroelectric phase stability, raman spectra were measured over the wavenumber range of 10-1000cm -1, as shown in FIG. 7 (a). The distribution of the raman bands follows that of the NaNbO 3 bands. In the wavenumber range of 100-300cm -1, the raman spectra of all ceramics exhibit multiple complex peaks, which are characteristic of low-symmetry antiferroelectric structures. Bands below 100cm -1 are associated with cationic translational movement at the a-position, while all other bands are associated with BO 6 octahedra in the ABO 3 perovskite structure. Significant changes in the raman spectroscopy shape of NN-10kBS may be associated with the presence of R-phase as shown in fig. 2. Respectively represents a double degenerate symmetry O-Nb/Sn-O stretching vibration and a triple degenerate symmetry O-Nb/Sn-O bending vibration. The v 5 band intensity decreases with increasing KBS concentration, reflecting a decrease in Nb 5+/Sn4+ ion displacement and (Nb, sn) O 6 octahedral tilt, due to lower average polarization at the B-site. The reduced tilt of the (Nb, sn) O 6 octahedron also manifests as a reduction in band intensity of v 5. The research of the embodiment of the invention finds that the reduction of the tilt of the octahedra of the BO 6 is possibly beneficial to the antiferroelectric phase stability of NN-based ceramics. By fitting the raman bands to the lorentz band shape, a v 5 band position of x=4% -8% was obtained, as shown in fig. 7 (b). As KBS concentration increases, band position shifts toward low wavenumber directions, which may be related to enhanced antiferroelectricity, similar to that of AgNbO 3 and NaNbO 3 -based ceramics. Although the tolerance factor of KBS (t KBS =0.978) is higher than that of NN (t NN =0.967), it is expected that the stability of antiferroelectric phase in NN-100xKBS ceramic will decrease with increasing x, but XRD refinement, electric hysteresis loop (P-E) and raman spectra together indicate an increase in stability of antiferroelectric phase. This can be achieved by using Sn 4+ Substituted Nb 5+/>While decreasing the average polarizability of the B site is explained by the decrease in the B site cation displacement and the tilt of the BO 6 octahedra, which enhances antiferroelectric stability.
Second aspect
Although NN-6KBS ceramics have a stable antiferroelectric phase and associated characteristic double hysteresis loops, the stability of the field-induced ferroelectric phase is still significant, resulting in a relatively high P r of 5 μC/cm 2 and a low E FA of 34kV/cm. Antiferroelectric ceramics of high P max, low P r, and high E FA are desirable from an energy storage standpoint. The energy storage density, i.e., the recovered energy density (W rec) and the energy efficiency (. Eta.), can be calculated from the hysteresis loop (P-E), as shown in FIG. 6, for 250kV/cm NN-6KBS, the schematic diagrams are 1.8J/cm 3 and 31%, respectively. Therefore, a defect engineering strategy is adopted, namely La 3+ is used for replacing Na +, so that the stability of the ferroelectric phase of the field can be reduced, and the energy storage performance of NN-6KBS can be improved. Two sets of NN-6KBS ceramics were prepared with La 3+ doped on different cation vacancies, denoted 100yLa-VA and 100yLa-VB, respectively. FIG. 8 (a) shows XRD patterns of La 3+ doped NN-6KBS and pure NN-6KBS (also referred to as 0 La). Impurity phases SnO 2 and K 3NbO4 were observed in the 100yLa-VA ceramic, whereas no impurity phase was observed in the 100yLa-VB ceramic. This difference may be due to the different cation vacancy content in the two groups of ceramic materials after doping with yLa 3+, the cation vacancy content in 100yLa-VA being 2y and the cation vacancy content in 100yLa-VB being 0.4y. The effect of La 3+ concentration on dielectric properties was similar in both groups of ceramic materials. Impurity phases can also be observed in SEM images of 100yLa-VA ceramics, as shown in FIG. 9. Notably, although no impurity phase was detected by XRD for 1.0% y.ltoreq.2.0% of the 100yLa-VB ceramic, small impurity particles could be observed in its SEM image, as shown in FIG. 10. When y is less than or equal to 1.0%, the dielectric peak in the high temperature region moves to the low temperature region, and when y is more than or equal to 1.5%, the dielectric peak suddenly moves to below 0 ℃ and becomes diffuse. Similar to NN-10KBS, increased relaxation properties can be expected to occur in ceramic materials with y.gtoreq.1.5%. The hysteresis loops (P-E) of these two sets of ceramic materials are shown in fig. 11. The ferroelectric hysteresis loops (P-E) of the ceramic materials with y=0.5% and 1.0% exhibit antiferroelectric characteristics with reduced P max compared to the pure NN-6 KBS. y=1.5% and 2.0% of the ceramic material exhibits a relaxation behavior like the hysteresis loop (P-E) of NN-10 KBS.
FIG. 12 (a) compares the monopolar hysteresis loop (P-E) of the above ceramic material with the bipolar hysteresis loop measured at 250 kV/cm. All La doped ceramic materials showed a decrease in P max, indicating that the stability of the ferroelectric phase was destroyed by La 3+ doping and cation vacancies. However, for La doped ceramic materials, the effect of cation vacancy positions on phase stability and hysteresis loop (P-E) shape is different. The phase transition electric fields E AF and E FA of 0.5La-VA were slightly reduced compared to the pure NN-6KBS, while the phase transition electric field of 0.5La-VB was significantly increased, as shown in FIG. 12 (b). The enhanced phase transition electric field indicates reduced field ferroelectric phase stability and improved antiferroelectric phase stability, possibly as a result of the combined action of a-site aliovalent La 3+ and B-site Nb vacancies. Thus, P r of 0.5La-VB is lower than other ceramic materials, about 0.6 μC/cm 2, which is advantageous for achieving high energy storage properties, as shown in FIG. 12 (C). It can be seen that the 0.5% La-VB phase transition electric field is the highest, and the residual polarization intensity P r is the lowest, so that the comprehensive energy storage performance is the best.
As shown in FIG. 13 (a), the unipolar hysteresis loop (P-E) of the 0.5La-VB ceramic was measured under different electric fields until it broke down. With the increase of the applied electric field, the change of the phase transition electric field E AF is small, which indicates that the antiferroelectric phase stability is insensitive to the applied electric field. The stability of the ferroelectric phase increases with increasing applied electric field, as evidenced by a decrease in the phase transition electric field E FA. The increase in ferroelectric phase stability results in a decrease in η at high electric fields. As shown in fig. 13 (b), as the electric field is further increased, the electric field strength remains unchanged, resulting in a steady rise of W rec, and a steady η. Although high electric fields favor the formation of ferroelectric phases, most of the field-induced ferroelectric phases still return to the original antiferroelectric phase at a high electric field of 610kV/cm, as evidenced by a low P r of 3 μC/cm 2. Thus, high W rec of 4.5J/cm 3 and a moderate η of 44% are obtained at 610kV/cm, which is superior to most of the reported NN-based antiferroelectric ceramics [13,14,15,16-18] and comparable to some well developed AN-based antiferroelectric ceramics [1-4,5,6,7-12], as shown in fig. 13 (c). The high energy storage performance of 0.5La-VB was attributed to the dense microstructure of the impurity-free phase shown in fig. 10 (a) and the high breakdown strength shown in fig. 14.
For practical energy storage applications, temperature stability and performance reliability are always important. As shown in FIG. 13 (d), the hysteresis loop (P-E) of the 0.5La-VB ceramic was measured in the temperature range of 30-180 ℃. As the measured temperature increases, the phase transition electric field E AF decreases, indicating a decrease in antiferroelectric phase stability at high temperatures. In contrast, P max is similar to E FA, indicating that field ferroelectrics are less sensitive to temperature relative to antiferroelectrics, which may be associated with high applied electric field enhanced ferroelectric phases. Therefore, both W rec and η increase with an increase in temperature, as shown in fig. 13 (e). Furthermore, the hysteresis loops (P-E) measured at 400kV/cm and the corresponding energy storage characteristics after different cycles are shown in FIGS. 13 (f) and (g), respectively. W rec and η remained stable after 105 cycles with less than 3% change. The high-temperature stability and the cycle reliability show that the 0.5La-VB ceramic has good high-temperature energy storage application prospect.
As a result, the stability of the antiferroelectric phase is improved with increasing x, XRD refinement, hysteresis loop (P-E) measurement and Raman spectroscopy confirm this, the improvement in antiferroelectric properties is attributed to the reduction in average B-site polarizability.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (13)
1. A sodium niobate-based antiferroelectric ceramic material characterized in that the ceramic material has the chemical formula:
(Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, where x=4% -10%;
or (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, where y=0.5% -2%;
or (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, where y=0.5% -2%).
2. The sodium niobate-based antiferroelectric ceramic material of claim 1, wherein the ceramic material has the formula: (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, where x=6% -8%.
3. A sodium niobate-based antiferroelectric ceramic material according to claim 2, characterized in that x = 6%.
4. The sodium niobate-based antiferroelectric ceramic material of claim 1, wherein the ceramic material has the formula: (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3, where y=0.5% -1.0%).
5. The sodium niobate-based antiferroelectric ceramic material of claim 4, wherein y = 0.5%.
6. The sodium niobate-based antiferroelectric ceramic material of claim 1, wherein the ceramic material has the formula: (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, where y=0.5% -1.0%).
7. The sodium niobate-based antiferroelectric ceramic material of claim 6, wherein y = 0.5%.
8. A method for preparing a sodium niobate-based antiferroelectric ceramic material according to any one of claims 1 to 7, comprising the steps of:
(1) When the chemical formula of the ceramic material is (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3, na 2CO3、K2CO3、Bi2O3、Nb2O5 and SnO 2 are used as raw materials, when the chemical formula of the ceramic material is (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 or (Na 0.94-yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3, Na2CO3、K2CO3、Bi2O3、Nb2O5、SnO2 and La 2O3 are used as raw materials, the raw materials are mixed according to the stoichiometric ratio of the ceramic material to obtain a raw material mixture, and then the raw material mixture is subjected to ball milling treatment for the first time to obtain raw material mixed powder;
(2) Calcining the raw material mixed powder to obtain ceramic powder;
(3) Performing secondary ball milling treatment on the ceramic powder, and then pressing the ceramic powder into ceramic sheets;
(4) Performing cold isostatic pressing treatment on the ceramic sheet to obtain a ceramic blank;
(5) And sintering the ceramic blank to obtain the ceramic material.
9. The method for producing a sodium niobate-based antiferroelectric ceramic material according to claim 8, wherein in the step (2), the temperature of the calcination treatment is 880 ℃ to 920 ℃; and/or the calcination treatment is carried out for 3-5 hours.
10. The method for preparing a sodium niobate-based antiferroelectric ceramic material according to claim 8, wherein in the step (3), the time of the secondary ball milling treatment is 20h to 28h; and/or the ceramic sheet has a diameter of 8mm to 12mm.
11. The method for producing a sodium niobate-based antiferroelectric ceramic material according to claim 8, wherein in the step (4), the pressure of the cold isostatic pressing treatment is 200MPa to 300MPa.
12. The method according to claim 8, wherein in the step (5), the sintering treatment is performed at a temperature of 1050 ℃ to 1200 ℃ when the ceramic material has a chemical formula (Na 1-xK0.5xBi0.5x)(Nb1-xSnx)O3), and at a temperature of 1270 ℃ to 1300 ℃ when the ceramic material has a chemical formula (Na 0.94-3yLayK0.03Bi0.03)(Nb0.94Sn0.06)O3 or (Na 0.94- yLayK0.03Bi0.03)(Nb0.94-0.4ySn0.06)O3).
13. A capacitor, characterized in that the dielectric material of the capacitor is the ceramic material according to any one of claims 1 to 7 or the ceramic material prepared by the preparation method according to any one of claims 8 to 12.
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