CN113185288A - Novel sodium niobate-based ceramic material and preparation method thereof - Google Patents
Novel sodium niobate-based ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 29
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 40
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 238000004321 preservation Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 8
- 238000004458 analytical method Methods 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 238000012360 testing method Methods 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 239000003292 glue Substances 0.000 claims abstract description 6
- 238000005469 granulation Methods 0.000 claims abstract description 6
- 230000003179 granulation Effects 0.000 claims abstract description 6
- 238000012216 screening Methods 0.000 claims abstract description 5
- 229910003378 NaNbO3 Inorganic materials 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000004146 energy storage Methods 0.000 abstract description 34
- 239000012071 phase Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a novel sodium niobate-based ceramic material and a preparation method thereof, and the method comprises the following steps: preparation of NaNbO3‑0.1Bi(Ni0.5Zr0.5)O3Powder; preparation of (Bi)0.5Na0.5)0.7Sr0.3TiO3A main crystalline phase; respectively weighing 0.6-1mol of the 0.9NaNbO3‑0.1Bi(Ni0.5Zr0.5)O3Powder, 0-0.1mol of (Bi)0.5Na0.5)0.7Sr0.3TiO3Mixing the main crystal phases to form a mixture; pouring the mixture into a ball milling tank for carrying out wet ball milling at a rotating speed, drying and screening after mixing and grinding to obtain dried powder, adding polyvinyl alcohol into the dried powder for granulation, pressing into a cylinder, and then carrying out glue discharging; after the binder removal is finished, sintering and heat preservation are carried out to obtain a ceramic sample, and then test analysis is carried out, wherein the ceramic sample is as follows: 0.6{0.9NaNbO3‑0.1Bi(Ni0.5Zr0.5)O3}‑0.4(Bi0.5Na0.5)0.7Sr0.3TiO3. The novel sodium niobate-based ceramic material prepared by the invention has high energy storage density and high efficiency, and has excellent thermal stability, frequency stability and good fatigue durability.
Description
Technical Field
The invention relates to the field of dielectric ceramic material energy storage, in particular to a novel sodium niobate-based ceramic material and a preparation method thereof.
Background
In recent years, dielectric capacitors for electrical energy storage have ultrahigh power density due to their ultra-fast charge/discharge rate compared to fuel cells and lithium ion batteries, and thus have been widely studied generally, large saturation polarization (P)S) High breakdown strength (BDS) and low remanent polarization (P)r) Is crucial for achieving high energy storage densities. Currently, there are four representative dielectric materials for energy storage applications: linear Dielectrics (LDs), Ferroelectrics (FEs), relaxor ferroelectrics (REFs) and Antiferroelectrics (AFEs). LDs materials typically have a high BDS and a small PrBut low PSLimiting their use in high energy storage. Meanwhile, FE is due to large PrEnergy storage density, although high polarization and dielectric of FE are desirable for energy storage characteristics. Has medium BDS and high PSNegligible PrAlways achieve high energy storage density. However, lead is a harmful element, seriously harming human health and the environment. Therefore, REFs are considered to be the most promising candidates for energy storage applications. In view of the above, it is necessary to provide a novel sodium niobate-based ceramic material and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a novel sodium niobate-based ceramic material which has high energy storage density and high efficiency, excellent thermal stability, excellent frequency stability and excellent fatigue durability, and a preparation method thereof.
In order to achieve the purpose, the novel sodium niobate-based ceramic material adopted by the invention has a chemical composition formula as follows: (1-x) [0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3]-x(Bi0.5Na0.5)0.7Sr0.3TiO3Wherein x is a molar ratio, and x is more than or equal to 0 and less than or equal to 0.40.
The invention also provides a preparation method of the novel sodium niobate-based ceramic material, which comprises the following steps:
preparation of NaNbO3-0.1Bi(Ni0.5Zr0.5)O3Powder;
preparation of (Bi)0.5Na0.5)0.7Sr0.3TiO3A main crystalline phase;
respectively weighing 0.6-1mol of the 0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3Powder, 0-0.1mol of (Bi)0.5Na0.5)0.7Sr0.3TiO3Mixing the main crystal phases to form a mixture;
pouring the mixture into a ball milling tank for carrying out wet ball milling at a rotating speed, drying and screening after mixing and grinding to obtain dried powder, adding polyvinyl alcohol into the dried powder for granulation, pressing into a cylinder, and then carrying out glue discharging;
after the binder removal is finished, sintering and heat preservation are carried out to obtain a ceramic sample, and then test analysis is carried out, wherein the ceramic sample is as follows: 0.6{0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3}-0.4(Bi0.5Na0.5)0.7Sr0.3TiO3。
Wherein 0.5mol Na was weighed2CO3、0.5molNb2O5Mixing, presintering and preserving heat to form NaNbO3A main crystalline phase;
weigh 0.5mol Bi2O3、0.5molNiO、0.5molZrO2Mixing, presintering and maintaining the temperature to form Bi (Ni)0.5Zr0.5)O3A main crystalline phase;
weighing 0.9mol of the NaNbO3Main crystal phase, 0.1mol of Bi (Ni)0.5Zr0.5)O3The main crystal phases are respectively mixed to form 0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3And (3) powder.
Wherein 0.5mol Na was weighed2CO3、0.5molNb2O5Mixing, presintering and preserving heat to form NaNbO3In the step of the main crystal phase:
the presintering temperature is 850 ℃, and the heat preservation time is 6 h.
Wherein 0.5mol Bi was weighed2O3、0.5molNiO、0.5molZrO2Mixing, presintering and maintaining the temperature to form Bi (Ni)0.5Zr0.5)O3In the step of the main crystal phase:
the presintering temperature is 720 ℃, and the heat preservation time is 4 h.
Wherein (Bi) is prepared0.5Na0.5)0.7Sr0.3TiO3A primary crystalline phase comprising:
weigh 0.175mol Bi2O3、0.175molNa2CO3、0.3molSrCO3、1molTiO2Respectively mixed, presintered and thermally insulated to form (Bi)0.5Na0.5)0.7Sr0.3TiO3A main crystal phase.
Wherein 0.175mol Bi was weighed2O3、0.175molNa2CO3、0.3molSrCO3、1molTiO2Respectively mixed, presintered and thermally insulated to form (Bi)0.5Na0.5)0.7Sr0.3TiO3In the step of the main crystal phase:
the presintering temperature is 850 ℃, and the heat preservation time is 4 hours.
Pouring the mixture into a ball milling tank for wet ball milling at a rotating speed:
the ball milling speed is 250r/min, and the ball milling time is 4 h.
Wherein, the step of mixing, grinding and drying comprises the following steps:
the drying temperature is as follows: 100 ℃ and 130 ℃.
After the glue discharging is finished, sintering and heat preservation are carried out, and a ceramic sample is obtained:
the pre-sintering temperature is 1240 ℃ plus 1260 ℃, and the heat preservation time is 2 h.
The invention has the beneficial effects that:
(1-x)[0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3]-xmol％(Bi0.5Na0.5)0.7Sr0.3TiO3(x is more than or equal to 0 and less than or equal to 0.40), wherein x is a molar ratio and x is more than or equal to 0 and less than or equal to 0.40. The results show that the ceramic has a higher energy storage density (6.43J/cm) when x is 0.43) And energy storage efficiency (82%). Meanwhile, a relatively stable energy storage density can be maintained within the temperature range of 20-180 ℃. The novel sodium niobate-based ceramic material prepared by the invention has high energy storage density and high efficiency, and has excellent thermal stability, frequency stability and good fatigue durability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a flow chart showing the steps of the method for preparing the novel sodium niobate-based ceramic material of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships illustrated in the drawings, and are used merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, are not to be construed as limiting the present invention. Further, in the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Referring to fig. 1, the present invention provides a novel sodium niobate-based ceramic material, which has a chemical composition formula: (1-x) [0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3]-x(Bi0.5Na0.5)0.7Sr0.3TiO3Wherein x is a molar ratio, and x is more than or equal to 0 and less than or equal to 0.40.
The invention also provides a preparation method of the novel sodium niobate-based ceramic material, which comprises the following steps:
s1: preparation of NaNbO3-0.1Bi(Ni0.5Zr0.5)O3Powder;
s2: preparation of (Bi)0.5Na0.5)0.7Sr0.3TiO3A main crystalline phase;
s3: respectively weighing 0.6-1mol of the 0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3Powder, 0-0.1mol of (Bi)0.5Na0.5)0.7Sr0.3TiO3Mixing the main crystal phases to form a mixture;
s4: pouring the mixture into a ball milling tank for carrying out wet ball milling at a rotating speed, drying and screening after mixing and grinding to obtain dried powder, adding polyvinyl alcohol into the dried powder for granulation, pressing into a cylinder, and then carrying out glue discharging;
s5: after the binder removal is finished, sintering and heat preservation are carried out to obtain a ceramic sample, and then test analysis is carried out, wherein the ceramic sample is as follows: 0.6{0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3}-0.4(Bi0.5Na0.5)0.7Sr0.3TiO3(hereinafter referred to as NN-BNZ-BNST).
In this embodiment, NaNbO is prepared3-0.1Bi(Ni0.5Zr0.5)O3A powder comprising: weigh 0.5mol Na2CO3、0.5molNb2O5Mixing, presintering and preserving heat to form NaNbO3A main crystalline phase; weigh 0.5mol Bi2O3、0.5molNiO、0.5molZrO2Mixing, presintering and maintaining the temperature to form Bi (Ni)0.5Zr0.5)O3A main crystalline phase; weighing 0.9mol of the NaNbO3Main crystal phase, 0.1mol of Bi (Ni)0.5Zr0.5)O3The main crystal phases are respectively mixed to form 0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3And (3) powder.
Weigh 0.5mol Na2CO3、0.5molNb2O5Mixing, presintering and preserving heat to form NaNbO3In the step of the main crystal phase: the presintering temperature is 850 ℃, and the heat preservation time is 6 h.
Weigh 0.5mol Bi2O3、0.5molNiO、0.5molZrO2Mixing, presintering and maintaining the temperature to form Bi (Ni)0.5Zr0.5)O3In the step of the main crystal phase: the presintering temperature is 720 ℃, and the heat preservation time is 4 h.
Preparation of (Bi)0.5Na0.5)0.7Sr0.3TiO3A primary crystalline phase comprising:
weigh 0.175mol Bi2O3、0.175molNa2CO3、0.3molSrCO3、1molTiO2Respectively mixed, presintered and thermally insulated to form (Bi)0.5Na0.5)0.7Sr0.3TiO3A main crystal phase.
Weigh 0.175mol Bi2O3、0.175molNa2CO3、0.3molSrCO3、1molTiO2Respectively mixed, presintered and thermally insulated to form (Bi)0.5Na0.5)0.7Sr0.3TiO3In the step of the main crystal phase: the presintering temperature is 850 ℃, and the heat preservation time is 4 hours.
Pouring the mixture into a ball milling tank for wet ball milling at a rotating speed: the ball milling speed is 250r/min, and the ball milling time is 4 h.
The steps of mixing, grinding and drying are as follows: the drying temperature is as follows: 100 ℃ and 130 ℃.
After the binder removal is finished, sintering and heat preservation are carried out, and a ceramic sample is obtained: the pre-sintering temperature is 1240 ℃ plus 1260 ℃, and the heat preservation time is 2 h.
Mixing, grinding, drying and screening to obtain dried powder: the dried objects pass through a 60-mesh screen and a 200-mesh screen in sequence.
Then adding polyvinyl alcohol into the dried powder for granulation and then pressing into a cylinder:
adding 6 wt% of polyvinyl alcohol; pressing the powder into a cylinder with the diameter of 6mm and the thickness of 3 mm.
The rubber discharging step is carried out: glue is discharged for 4h at 550 ℃, and the heating rate is 1 ℃/min.
After the binder removal is finished, sintering and heat preservation are carried out to obtain a ceramic sample, and then the steps of testing and analyzing are carried out: sintering at 1240-1260 ℃ at a heating rate of 5 ℃/min and preserving heat for 2h to obtain a ceramic sample.
The method specifically comprises the following steps: weigh 0.5mol Na2CO3、0.5molNb2O5Mixing, presintering at 850 deg.C for 6 hr to obtain NaNbO3A main crystalline phase; weigh 0.5mol Bi2O3、0.5molNiO、0.5molZrO2Mixing, presintering at 720 deg.C for 4 hr to obtain Bi (Ni)0.5Zr0.5)O3A main crystalline phase; weigh 0.175mol Bi2O3、0.175molNa2CO3、0.3molSrCO3、1molTiO2Respectively mixing, presintering at 850 deg.C for 4 hr to obtain (Bi)0.5Na0.5)0.7Sr0.3TiO3A main crystalline phase; d, weigh 0.9mol of NaNbO3、0.1molBi(Ni0.5Zr0.5)O3Respectively, are mixed to form 0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3Powder; 0.9NaNbO was weighed in the following Table 13-0.1Bi(Ni0.5Zr0.5)O3、(Bi0.5Na0.5)0.7Sr0.3TiO3Mixing;
table 1 is as follows:
pouring the mixture into a ball milling tank for wet ball milling for 4 hours at the rotating speed of 250r/min, mixing and grinding the mixture, quickly drying the mixture at the temperature of 100-130 ℃, sieving the mixture by a 60-mesh and 200-mesh sieve,
and adding 6 wt% of polyvinyl alcohol (PVA) into the dried powder for granulation, pressing the powder into a small cylinder with the diameter of 6mm and the thickness of 3mm, and carrying out gel discharge at 550 ℃ for 4 hours at the temperature rise rate of 1 ℃/min.
Then sintering at 1240-1260 ℃ at the heating rate of 5 ℃/min and preserving the heat for 2h to obtain 0.6{0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3}-0.4(Bi0.5Na0.5)0.7Sr0.3TiO3A ceramic material.
Table 2 below lists 5 specific examples of the different components constituting the invention and their energy storage properties (the methods of preparation are as described above).
Table 2:
the lead-free dielectric ceramic material prepared by the invention has excellent energy storage. When x is 0.40, the ceramic has extremely high energy storage density (6.43J/cm)3) And energy storage efficiency (82%). This indicates that NN-BNZ-BNST ceramics can become a lead-free candidate material for new high energy storage applications.
In addition, in the process of obtaining a ceramic sample, and then performing test analysis: (the relevant test analysis method and the pass conditions are as follows).
a. The phase structure of the samples was compared with CuKa radiation (. lamda. ═ 0.15406nm) using X-ray powder diffraction analysis (X' Pert PRO; PA Nalytical, Almelo, Netherlands) and tested to be pseudo-cubic.
b. The microstructure of the sample was observed by a scanning electron microscope (JSM6380-LV SEM, JEOL, Tokyo, Japan), and the sample was tested for surface densification of 95% and an average grain size of about 5 μm.
c. The relative dielectric constant and loss tangent of the ceramic were measured using a precision impedance analyzer (4294A, Hewlett-Packard Co, Palo alto, Calif.) at a heating rate of 2 deg.C/minute over a temperature range of-160 deg.C to 180 deg.C, and the dielectric constant of the sample was determined to be about 580 at 25 deg.C. The sample is polished to a thickness of 0.3 + -0.05 mm during sample preparation, and a double-sided silver electrode is coated.
d. The polarization hysteresis loop is measured by a ferroelectric material parameter tester (RT66, radial Technologies, NM, USA). To better characterize the energy storage performance, the sintered samples were polished to a thickness of 0.15 ± 0.01 mm and coated with a silver electrode having a diameter of 2 mm. The breakdown electric field of the sample should reach 530kV/cm, and the recoverable energy storage density should reach 6.43J/cm3The energy storage efficiency should reach 82%.
The invention adopts a solid-phase synthesis method, and wet ball milling is carried out in a certain ethanol solution to obtain raw powder with fine particles and uniform particle size; the high-performance relaxation ferroelectric lead-free energy storage ceramic is prepared by adopting a heat treatment sintering process. The solid solution ceramic material prepared by the novel optimized process has the advantages that the sintering temperature is lower (less than or equal to 1300 ℃), the relative density is more than or equal to 96 percent, the average grain size is gradually reduced along with the increase of the components, and the recoverable energy storage density (W) is greatly improvedrec) And energy storage efficiency (η). The method inhibits the formation of oxygen vacancy, enhances the insulation property and obviously optimizes the NaNbO3The stability of the energy storage characteristic of the base ceramic has great commercial application prospect.
In summary, the following steps: the design of the invention is as follows:
(1-x)[0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3]-xmol％(Bi0.5Na0.5)0.7Sr0.3TiO3(x is more than or equal to 0 and less than or equal to 0.40), wherein x is a molar ratio and x is more than or equal to 0 and less than or equal to 0.40. The results show that the ceramic has a higher energy storage density (6.43J/cm) when x is 0.43) And energy storage efficiency (82%). Meanwhile, a relatively stable energy storage density can be maintained within the temperature range of 20-180 ℃. Therefore, the lead-free solid solution of NN-BNZ-BNST is expected to become a promising high-energy storage pulse power capacitor.
Further: the invention introduces strong ferroelectric Bi (Ni)0.5Zr0.5)O3And (Bi)0.5Na0.5)0.7Sr0.3TiO3With NaNbO3The antiferroelectric forms a uniform solid solution to improve the maximum polarization strength and breakdown field strength of the ceramic material, thereby obtaining a dielectric ceramic material with high energy storage density.
Bi (Ni) introduced by the invention0.5Zr0.5)O3And (Bi)0.5Na0.5)0.7Sr0.3TiO3Has the following advantages: high insulating TiO2And Ni having a small ionic radius+The introduction of the NaNbO greatly improves the NaNbO3May be due to reduced sodium volatilization and oxygen vacancy formation, reduced dielectric loss and leakage current, and enhanced cationic disorder.
Bi(Ni0.5Zr0.5)O3The introduction of (A) can promote NaNbO3The sintering of the ceramic obviously reduces the porosity and the grain size, thereby obtaining high breakdown strength.
By adding NaNbO3Introduction of Bi (Ni) into the matrix0.5Zr0.5)O3And (Bi)0.5Na0.5)0.7Sr0.3TiO3Form A-site and B-site ion disorder, destroy ferroelectric long-range order, and convert ferroelectric domain into polar nano micro region. The rapid response of the polar nano micro-area under an external electric field is utilized to remarkably improve the energy storage density and the energy storage efficiency of the material.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A novel sodium niobate-based ceramic material, which is characterized in that,
the chemical composition formula is as follows: (1-x) [0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3]-x(Bi0.5Na0.5)0.7Sr0.3TiO3Wherein x is a molar ratio, and x is more than or equal to 0 and less than or equal to 0.40.
2. The method for producing a novel sodium niobate-based ceramic material according to claim 1, comprising the steps of:
preparation of NaNbO3-0.1Bi(Ni0.5Zr0.5)O3Powder;
preparation of (Bi)0.5Na0.5)0.7Sr0.3TiO3A main crystalline phase;
respectively weighing 0.6-1mol of the 0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3Powder, 0-0.1mol of (Bi)0.5Na0.5)0.7Sr0.3TiO3Mixing the main crystal phases to form a mixture;
pouring the mixture into a ball milling tank for carrying out wet ball milling at a rotating speed, drying and screening after mixing and grinding to obtain dried powder, adding polyvinyl alcohol into the dried powder for granulation, pressing into a cylinder, and then carrying out glue discharging;
after the binder removal is finished, sintering and heat preservation are carried out to obtain a ceramic sample, and then test analysis is carried out, wherein the ceramic sample is as follows: 0.6{0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3}-0.4(Bi0.5Na0.5)0.7Sr0.3TiO3。
3. The method for producing a novel sodium niobate-based ceramic material according to claim 2, wherein NaNbO is produced3-0.1Bi(Ni0.5Zr0.5)O3A powder comprising:
weigh 0.5mol Na2CO3、0.5molNb2O5Mixing, presintering and preserving heat to form NaNbO3A main crystalline phase;
weigh 0.5mol Bi2O3、0.5molNiO、0.5molZrO2Mixing, presintering and keeping warmFormation of Bi (Ni)0.5Zr0.5)O3A main crystalline phase;
weighing 0.9mol of the NaNbO3Main crystal phase, 0.1mol of Bi (Ni)0.5Zr0.5)O3The main crystal phases are respectively mixed to form 0.9NaNbO3-0.1Bi(Ni0.5Zr0.5)O3And (3) powder.
4. The process for producing a novel sodium niobate-based ceramic material according to claim 3, wherein 0.5mol of Na is weighed2CO3、0.5molNb2O5Mixing, presintering and preserving heat to form NaNbO3In the step of the main crystal phase:
the presintering temperature is 850 ℃, and the heat preservation time is 6 h.
5. The process for producing a novel sodium niobate-based ceramic material according to claim 3, wherein 0.5mol of Bi is weighed2O3、0.5molNiO、0.5molZrO2Mixing, presintering and maintaining the temperature to form Bi (Ni)0.5Zr0.5)O3In the step of the main crystal phase:
the presintering temperature is 720 ℃, and the heat preservation time is 4 h.
6. The method for producing a novel sodium niobate-based ceramic material according to claim 3, wherein (Bi) is produced0.5Na0.5)0.7Sr0.3TiO3A primary crystalline phase comprising:
weigh 0.175mol Bi2O3、0.175molNa2CO3、0.3molSrCO3、1molTiO2Respectively mixed, presintered and thermally insulated to form (Bi)0.5Na0.5)0.7Sr0.3TiO3A main crystal phase.
7. The method for producing a novel sodium niobate-based ceramic material according to claim 6, wherein 0.175mol bi is weighed2O3、0.175molNa2CO3、0.3molSrCO3、1molTiO2Respectively mixed, presintered and thermally insulated to form (Bi)0.5Na0.5)0.7Sr0.3TiO3In the step of the main crystal phase:
the presintering temperature is 850 ℃, and the heat preservation time is 4 hours.
8. The method for preparing a novel sodium niobate-based ceramic material according to claim 2, wherein the step of pouring the mixture into a ball milling tank for wet ball milling at a rotating speed comprises:
the ball milling speed is 250r/min, and the ball milling time is 4 h.
9. The method for preparing a novel sodium niobate-based ceramic material according to claim 2, wherein the step of mixing, grinding and then drying:
the drying temperature is as follows: 100 ℃ and 130 ℃.
10. The method for preparing a novel sodium niobate-based ceramic material according to claim 2, wherein after the binder removal is completed, the sintering and heat preservation are performed to obtain a ceramic sample, wherein the method comprises the following steps:
the pre-sintering temperature is 1240 ℃ plus 1260 ℃, and the heat preservation time is 2 h.
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