CN110015894B - Sodium bismuth titanate-based ceramic with high dielectric stability at high temperature and preparation method and application thereof - Google Patents
Sodium bismuth titanate-based ceramic with high dielectric stability at high temperature and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 59
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 17
- 239000003990 capacitor Substances 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 3
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 44
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract 1
- 239000010955 niobium Substances 0.000 description 21
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 8
- 239000004677 Nylon Substances 0.000 description 7
- 229910052758 niobium Inorganic materials 0.000 description 7
- 229920001778 nylon Polymers 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 229910052701 rubidium Inorganic materials 0.000 description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UDRRLPGVCZOTQW-UHFFFAOYSA-N bismuth lead Chemical compound [Pb].[Bi] UDRRLPGVCZOTQW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention discloses a sodium bismuth titanate-based ceramic with stable dielectric property at high temperature, a preparation method and application thereof, wherein the component raw material and the molar percentage content thereof are Bi0.35Na0.65‑ 0.5xRb0.5xTi0.7NbyO3(x is 0-0.05, y is 0.30), and the doped Rb with different contents is prepared by a solid-phase reaction method+、Nb5+Ion-doped sodium bismuth titanate-based ceramic powder; and then the final ceramic material is prepared by the processes of ball milling, cold press molding and sintering. Experimental results show that the relative density of the doped and modified material can reach more than 96% at about 1150 ℃, the capacitance temperature coefficient (TCC) of-40 ℃ to 400 ℃ can reach within 10%, and the dielectric loss (tan delta) is less than 0.05. The material has great potential as a high-temperature capacitor material. The preparation raw materials have wide sources, the cost is low, the preparation process is easy to implement and has good repeatability, and the requirement of large-scale production can be met.
Description
Technical Field
The invention relates to a sodium bismuth titanate-based ceramic with stable dielectric property at high temperature, a preparation method and application thereof, belonging to the field of electronic ceramics.
Background
With the rapid development of advanced electronic materials in the last decade, research on high-performance functional electronic components is attracting much attention. Accordingly, there is an increasing demand in the industry for capacitor materials. To date, due to the demand for severe operating environments (e.g., high temperatures, operating temperatures exceeding 200 ℃) in many industrial fields, more and more researchers are focusing on the development of materials suitable for electronic devices in high temperature environments. In order to meet the requirement for proper operation of the capacitor at high temperatures, the ceramic capacitor must satisfy the following requirements: (1) the dielectric constant is higher and the dielectric loss is lower in a use temperature range; (2) still have high resistivity at elevated temperatures in order to reduce leakage current; (3) the dielectric constant has high temperature stability in the use temperature range, and the Temperature Coefficient of Capacitance (TCC) is controlled within 15 percent. At present, the market of ceramic capacitors is still occupied by lead-containing perovskite-structured materials, such as lead magnesium niobate-based materials and lead zinc niobate-based materials. Such capacitor materials have large dielectric constants (10000-. Further research shows that the temperature stability is improved to a certain extent by placing the center of gravity on the bismuth-lead based ceramic material. However, these lead-containing materials are not environmentally friendly due to volatilization of lead vapor during high temperature preparation. With the increasing demands on environmental quality and human health, lead-containing materials need to be replaced by lead-free materials. How to modify the lead-free material by proper doping so that the lead-free material simultaneously meets the following conditions is a key problem influencing the practical application of the lead-free material in high-performance capacitors: high dielectric constant, low dielectric loss and wide temperature range of use.
As an alternative, sodium bismuth titanate (BNT, Bi)0.5Na0.5TiO3) Ceramic has recently received great attention because it has a large saturation polarization and superior dielectric properties. Due to Bi in BNT3+With Pb2+With similar lone pair 6s2And (4) effect. Thus, dielectric properties comparable to those of lead-containing materials can be obtained by appropriate doping. BNT is a perovskite type A-site ion composite substituted ferroelectric. A site is Bi3+、Na+Co-occupied, B position by Ti4+It occupies two dielectric peaks on the high temperature dielectric temperature spectrum. At present, the research of the domestic BNT system for preparing the ceramic capacitor is rarely reported.
Disclosure of Invention
In view of the disadvantages of the prior art, the first object of the present invention is to provide a sodium bismuth titanate-based ceramic having stable dielectric properties at high temperatures, which has low dielectric loss while having stable dielectric properties.
The second purpose of the invention is to provide a preparation method of the bismuth sodium titanate-based ceramic with stable dielectric property at high temperature.
The third object of the present invention is to provide the use of the above-mentioned sodium bismuth titanate-based ceramic having stable dielectric properties at high temperatures, and to apply it to high-temperature capacitors.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a sodium bismuth titanate-based ceramic with stable dielectric properties at high temperature, which comprises the following raw materials in percentage by mole: bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3，(x＝0-0.05，y＝0.30)。
The invention provides rubidium and niobium co-doped BNT-based ceramic for the first time, wherein Rb is used at the A site+To replace Na+With the aim of reducing Na+Volatilization in the preparation process improves the stability of the dielectric constant at high temperature. Nb in the B site5+Substitution at the B-position with the aim of overcoming Ti4+Reducing effect at high temperature to reduce material loss. The obtained rubidium and niobium codoped BNT-based ceramic shows the characteristics of typical relaxor ferroelectrics, the dielectric peak is widened, and the temperature stability of the dielectric constant (TCC) is improved<10%) and low dielectric loss (tan delta)<0.05)。
In the invention, the co-doping amount of rubidium and niobium is very important, for the substitution molar ratio of niobium, the inventor finally determines that the substitution molar ratio is 0.3 through a large amount of experiments, the material performance can be influenced if the value is too large or too small, the whole body still shows the relaxor ferroelectric property when the niobium element is less than 0.25, and the high-temperature dielectric property is unstable due to the fluctuation of a polar micro-region along with the temperature on a dielectric temperature spectrum. When the niobium element is more than 0.35, the entire composition exhibits paraelectric characteristics, and the dielectric constant is rapidly decreased due to the lack of ferroelectricity, resulting in a decrease in dielectric properties.
In a preferred scheme, the bismuth sodium titanate-based ceramic with stable dielectric property comprises the following raw materials in percentage by mole: bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3，(x＝0.01-0.04，y＝0.30)。
Preferably, the bismuth sodium titanate-based ceramic with stable dielectric properties comprises the following raw materials in percentage by mole: bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3，(x＝0.02、0.04，y＝0.30)。
In the present invention, when x is 0.02 or 0.04, the obtained bismuth sodium titanate-based ceramics have a Temperature Coefficient of Capacitance (TCC) of-40 ℃ to 400 ℃ of within 10%, have extremely excellent temperature stability, and have a dielectric loss (tan. delta) <0.05 in their temperature range of-200 ℃ to 290 ℃.
The invention relates to a preparation method of sodium bismuth titanate-based ceramic with stable dielectric property at high temperature, which comprises the following steps: according to Bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3Stoichiometric ratio of (x is 0-0.05, y is 0.30) to obtain Bi2O3,Na2CO3,TiO2,Nb2O5,Rb2CO3Obtaining a mixture, performing first ball milling on the mixture to obtain slurry A, pre-sintering the slurry A to obtain pre-sintered powder, performing second ball milling on the pre-sintered powder to obtain slurry B, performing press molding on the slurry B to obtain a green body, and sintering the green body to obtain the sodium bismuth titanate-based ceramic with stable dielectric property;
the pre-burning program comprises the following steps: firstly heating to 800 ℃ and 850 ℃, preserving the heat for 2-4h, then heating to 900 ℃ and 950 ℃, and preserving the heat for 4-6 h.
The inventor finds that the volatilization of bismuth element at high temperature can be effectively reduced by adopting the gradient pre-sintering, and the main crystal phase is synthesized by the pre-sintering.
In the actual experiment process, before the raw materials are prepared, the raw material powder needs to be put into an oven for drying, so that the moisture in the raw materials is fully volatilized, and the weighing error is prevented.
In the invention, wet ball milling is adopted, ball milling equipment can adopt conventional equipment in the prior art, such as a planetary ball mill, the ball milling medium is preferably alcohol, the grinding balls are preferably zirconia balls, and the ball milling is carried out in a nylon tank.
In a preferred scheme, in the first ball milling process, the mass ratio of the alcohol to the zirconia balls to the raw materials is 0.6-0.8: 2.5-3: 1, the ball milling speed is 300-.
The raw material is the prepared Bi2O3,Na2CO3,TiO2,Nb2O5,Rb2CO3。
And uniformly mixing the powder materials through primary ball milling to ensure that the sample fully reacts during pre-sintering, and drying the obtained slurry A after the ball milling is finished.
Preferably, the obtained slurry A is sieved by a 30-mesh sieve, and undersize products are taken and subjected to pre-sintering.
In the preferred scheme, in the second ball milling process, the mass ratio of the alcohol to the zirconia balls to the raw materials is 0.4-0.6: 2.5-3: 1, the ball milling speed is 300-.
And the secondary ball milling is carried out to further refine the powder, so that the powder is convenient to sinter after compression molding, and the obtained slurry B is dried after the ball milling is finished.
Preferably, the obtained slurry B is sieved by a 60-mesh sieve, and undersize products are taken and pressed to form.
Preferably, the pressure of the compression molding is 75-125MPa, and the pressure maintaining time is 1-2 min.
In the specific operation process, the dried slurry B is firstly placed in a forming die for preliminary press forming, and then is placed in a cold press for final press forming at a certain pressure and pressure maintaining time.
Preferably, the green body sintering procedure is as follows: the sintering temperature is 1125-1175 ℃, the heat preservation time is 3-5h, and the heating rate is 3-5 ℃/min.
Finally obtaining the ceramic with compact and uniform grain size by sintering.
The invention relates to an application of sodium bismuth titanate-based ceramic with stable dielectric property at high temperature, which is applied to a high-temperature capacitor.
The invention has the beneficial effects that:
1. the invention provides rubidium and niobium co-doped BNT-based ceramic for the first time, the obtained rubidium and niobium co-doped BNT-based ceramic has less defects, high compactness and good crystallinity, shows the characteristics of typical relaxor ferroelectrics, has a broadened dielectric peak, a high dielectric constant (>800), and improved temperature stability of the dielectric constant (TCC < 10%), and simultaneously has lower dielectric loss (tan delta <0.05), and has a wider temperature application range compared with a commercial X7R capacitor.
2. The high-temperature capacitor ceramic material prepared by the invention can completely meet the application requirements of electronic components such as pressure sensors, transducers and the like in the field of high-temperature environment, and has practical application value in high-temperature electronic equipment.
3. The preparation method is simple, the process is controllable, the raw materials are cheap, and the requirement of large-scale production can be met.
Drawings
FIG. 1 is an X-ray diffraction pattern of the sodium bismuth titanate-based ceramics obtained in examples 1 to 6, and it can be seen from the graphs that the samples obtained in examples 1 to 6 all exhibit a single perovskite structure and no second phase is found.
FIG. 2 is a scanning electron micrograph of the sodium bismuth titanate-based ceramics of examples 1 to 6, wherein. FIG. 2(a) is a scanning electron micrograph of a sodium bismuth titanate-based ceramic obtained in example 1, FIG. 2(b) is a scanning electron micrograph of a sodium bismuth titanate-based ceramic obtained in example 2, FIG. 2(c) is a scanning electron micrograph of a sodium bismuth titanate-based ceramic obtained in example 3, FIG. 2(d) is a scanning electron micrograph of a sodium bismuth titanate-based ceramic obtained in example 4, FIG. 2(e) is a scanning electron micrograph of a sodium bismuth titanate-based ceramic obtained in example 5, and FIG. 2(f) is a scanning electron micrograph of a sodium bismuth titanate-based ceramic obtained in example 6, and it can be seen from these photographs that the samples obtained in examples 1 to 6 are good in crystallinity, clear in grain boundaries, and high in density.
FIG. 3 is a dielectric temperature spectrum of a sodium bismuth titanate-based ceramic obtained in examples 1 to 6, wherein FIG. 3(a) is a dielectric temperature spectrum of a sodium bismuth titanate-based ceramic obtained in example 1, FIG. 3(b) is a dielectric temperature spectrum of a sodium bismuth titanate-based ceramic obtained in example 2, FIG. 3(c) is a dielectric temperature spectrum of a sodium bismuth titanate-based ceramic obtained in example 3, FIG. 3(d) is a dielectric temperature spectrum of a sodium bismuth titanate-based ceramic obtained in example 4, FIG. 3(e) is a dielectric temperature spectrum of a sodium bismuth titanate-based ceramic obtained in example 5, and FIG. 3(f) is a dielectric temperature spectrum of a sodium bismuth titanate-based ceramic obtained in example 6.
FIG. 4 is a Temperature Coefficient of Capacitance (TCC) of the sodium bismuth titanate-based ceramics of examples 1-6.
As can be seen, FIGS. 3 and 4 show the dielectric properties of all samples between-200 ℃ and 400 ℃, and all samples show strong dielectric peak broadening characteristics. The results are shown in table 1, and it can be seen that the rubidium/niobium co-doped BNT can reach a Temperature Coefficient of Capacitance (TCC) within 15% at-60 ℃ to 400 ℃ by the doping modification of the invention. Wherein examples 3 and 5, the Temperature Coefficient of Capacitance (TCC) at-40 ℃ to 400 ℃ can be achieved within 10%, while the dielectric loss (tan delta) is less than 0.05 in the range of-200 ℃ to 290 ℃.
TABLE 1 dielectric Properties of sodium bismuth titanate-based ceramics obtained in examples 1 to 6
| Example of the implementation | εr(25℃,1kHz) | ΔT,TCC≤15％(℃) | ΔT,TCC≤10％(℃) | ΔT,tanδ≤0.05(℃) |
| 1 | 922 | -86-366 | -60-240 | -200-286 |
| 2 | 865 | -95-400 | -68-369 | -200-285 |
| 3 | 932 | -70-400 | -44-400 | -200-299 |
| 4 | 965 | -77-400 | -54-238 | -200-160 |
| 5 | 1321 | -68-400 | -43-400 | -200-292 |
| 6 | 1028 | -64-300 | -52-171 | -200-232 |
Detailed Description
The present invention will be described in detail with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention are within the scope of the present invention.
Example 1
Raw materials are expressed as the general formula Bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3Weighing and proportioning (x is 0, y is 0.30), putting absolute ethyl alcohol as a dispersion medium into a nylon ball milling tank, ball milling for 4 hours by using a planetary ball mill at the rotating speed of 360r/min, baking for 12 hours on a hot table, continuously heating to 800 ℃ in a box type furnace, preserving heat for 2 hours, heating to 900 ℃ and preserving heat for 4 hours to obtain the bismuth sodium titanate-based ceramicAnd (3) porcelain powder. And carrying out secondary ball milling and drying on the synthesized ceramic powder under the same ball milling condition, sieving, pressing into a blank with the diameter of 13mm and the thickness of about 1mm, and sintering at 1150 ℃ for 3 h. And grinding, polishing and silvering the obtained sample, and then testing the dielectric property. Dielectric constant value epsilon at room temperaturer922, temperature range of-86-366 ℃ with Temperature Coefficient of Capacitance (TCC) less than 15%, temperature range of-60-240 ℃ with Temperature Coefficient of Capacitance (TCC) less than 10%, and resistivity of 1.50 x 106Ω·m。
Example 2
Raw materials are expressed as the general formula Bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3Weighing and proportioning (x is 0.01, y is 0.30), putting the materials into a nylon ball milling tank by taking absolute ethyl alcohol as a dispersion medium, ball milling the materials for 4 hours by using a planetary ball mill at the rotating speed of 360r/min, baking the materials on a hot table for 12 hours, continuously heating the materials to 800 ℃ in a box type furnace, preserving the heat for 2 hours, then heating the materials to 900 ℃, and preserving the heat for 4 hours to obtain the bismuth sodium titanate-based ceramic powder. And carrying out secondary ball milling and drying on the synthesized ceramic powder under the same ball milling condition, sieving, pressing into a blank with the diameter of 13mm and the thickness of about 1mm, and sintering at 1150 ℃ for 3 h. And grinding, polishing and silvering the obtained sample, and then testing the dielectric property. Dielectric constant value epsilon at room temperaturer865 deg.C, temperature range with capacitance temperature coefficient (TCC) less than 15% is-95 deg.C-400 deg.C, temperature range with capacitance temperature coefficient (TCC) less than 10% is-68 deg.C-369 deg.C, and resistivity is 1.85 × 106Ω·m。
Example 3
Raw materials are expressed as the general formula Bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3Weighing and proportioning (x is 0.02, y is 0.30), putting the materials into a nylon ball milling tank by taking absolute ethyl alcohol as a dispersion medium, ball milling the materials for 4 hours by using a planetary ball mill at the rotating speed of 360r/min, baking the materials on a hot table for 12 hours, continuously heating the materials to 800 ℃ in a box type furnace, preserving the heat for 2 hours, then heating the materials to 900 ℃, and preserving the heat for 4 hours to obtain the bismuth sodium titanate-based ceramic powder. Carrying out secondary ball milling, drying and sieving on the synthesized ceramic powder under the same ball milling conditionThen pressing into a blank with the diameter of 13mm and the thickness of about 1mm, and sintering for 3h at 1150 ℃. And grinding, polishing and silvering the obtained sample, and then testing the dielectric property. Dielectric constant value epsilon at room temperaturer932, a temperature range with a Temperature Coefficient of Capacitance (TCC) of less than 15% from-70 ℃ to 400 ℃, a temperature range with a Temperature Coefficient of Capacitance (TCC) of less than 10% from-44 ℃ to 400 ℃, and a resistivity of 2.33 x 106Ω·m。
Example 4
Raw materials are expressed as the general formula Bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3Weighing and proportioning (x is 0.03, y is 0.30), putting the materials into a nylon ball milling tank by taking absolute ethyl alcohol as a dispersion medium, ball milling the materials for 4 hours by using a planetary ball mill at the rotating speed of 360r/min, baking the materials on a hot table for 12 hours, continuously heating the materials to 800 ℃ in a box type furnace, preserving the heat for 2 hours, then heating the materials to 900 ℃, and preserving the heat for 4 hours to obtain the bismuth sodium titanate-based ceramic powder. And carrying out secondary ball milling and drying on the synthesized ceramic powder under the same ball milling condition, sieving, pressing into a blank with the diameter of 13mm and the thickness of about 1mm, and sintering at 1150 ℃ for 3 h. And grinding, polishing and silvering the obtained sample, and then testing the dielectric property. Dielectric constant value epsilon at room temperaturer965, temperature range with Temperature Coefficient of Capacitance (TCC) less than 15% is-77-400 deg.C, temperature range with Temperature Coefficient of Capacitance (TCC) less than 10% is-54-238 deg.C, and resistivity is 2.33 x 106Ω·m。
Example 5
Raw materials are expressed as the general formula Bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3Weighing and proportioning (x is 0.04, y is 0.30), putting the materials into a nylon ball milling tank by taking absolute ethyl alcohol as a dispersion medium, ball milling the materials for 4 hours by using a planetary ball mill at the rotating speed of 360r/min, baking the materials on a hot table for 12 hours, continuously heating the materials to 800 ℃ in a box type furnace, preserving the heat for 2 hours, then heating the materials to 900 ℃, and preserving the heat for 4 hours to obtain the bismuth sodium titanate-based ceramic powder. And carrying out secondary ball milling and drying on the synthesized ceramic powder under the same ball milling condition, sieving, pressing into a blank with the diameter of 13mm and the thickness of about 1mm, and sintering at 1150 ℃ for 3 h. The obtained sample is polished,Polishing and silver coating, and then performing dielectric property test. Dielectric constant value epsilon at room temperaturer1321, the temperature range with the Temperature Coefficient of Capacitance (TCC) less than 15 percent is-68-400 ℃, the temperature range with the Temperature Coefficient of Capacitance (TCC) less than 10 percent is-43-400 ℃, and the resistivity is 1.58 x 106Ω·m。
Example 6
Raw materials are expressed as the general formula Bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3Weighing and proportioning (x is 0.05, y is 0.30), putting the materials into a nylon ball milling tank by taking absolute ethyl alcohol as a dispersion medium, ball milling the materials for 4 hours by using a planetary ball mill at the rotating speed of 360r/min, baking the materials on a hot table for 12 hours, continuously heating the materials to 800 ℃ in a box type furnace, preserving the heat for 2 hours, then heating the materials to 900 ℃, and preserving the heat for 4 hours to obtain the bismuth sodium titanate-based ceramic powder. And carrying out secondary ball milling and drying on the synthesized ceramic powder under the same ball milling condition, sieving, pressing into a blank with the diameter of 13mm and the thickness of about 1mm, and sintering at 1150 ℃ for 3 h. And grinding, polishing and silvering the obtained sample, and then testing the dielectric property. Dielectric constant value epsilon at room temperaturer1028, temperature range with Temperature Coefficient of Capacitance (TCC) less than 15% from-64 ℃ to 400 ℃, temperature range with Temperature Coefficient of Capacitance (TCC) less than 10% from-52 ℃ to 171 ℃, and resistivity of 1.56 x 106Ω·m。
The above examples are carried out on the premise of the technical solution of the present invention, and detailed embodiments and operation procedures are given, but the scope of the present invention is not limited to the above examples.
Comparative example 1
Other conditions are the same as the example 3, only the doping content of the niobium element is changed, and the molecular formula of the ceramic material is changed into Bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3(x is 0.02, y is 0.20), and the obtained sample is subjected to a dielectric property test, although the dielectric constant of the sample is increased, the dielectric loss of the sample is increased, the frequency dependence is also enhanced, the temperature fluctuation is obviously increased, and the temperature stability is obviously reduced.
Comparative example 2
Other conditions andin the same manner as in example 3, the doping content of the niobium element was changed and the molecular formula of the ceramic material was changed to Bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3(x is 0.02, y is 0.40), and the obtained sample is tested for dielectric property, and although the dielectric loss is reduced, the dielectric constant is stable in a wider temperature range, but the dielectric constant is obviously reduced.
Comparative example 3
The other conditions are the same as the example 3, the A-site doping element is changed into the strontium element, and the molecular formula of the ceramic material is changed into Srx(Bi1-xNa1-x)0.5Ti0.7NbyO3(x is 0.20, y is 0.30), and the obtained sample is tested for dielectric properties, and although the dielectric constant of the sample is remarkably increased, two dielectric peaks appear on a dielectric temperature spectrum, the temperature stability is seriously deteriorated, and the dielectric loss is remarkably increased.
Comparative example 4
The other conditions are the same as the example 3, the molecular formula of the ceramic material is not changed, and the pre-sintering procedure is changed into one-step synthesis (800 ℃ for 2 h). The obtained sample is tested for dielectric property, a plurality of dielectric peaks appear on a dielectric temperature spectrum, the frequency dependence is obvious, the temperature stability is reduced, and the dielectric loss is obviously increased.
Comparative example 5
The other conditions are the same as the example 3, the molecular formula of the ceramic material is not changed, and the pre-sintering procedure is changed into one-step synthesis (900 ℃ for 4 hours). The obtained sample can not be sintered to be compact under the same condition, and the loss of stoichiometric ratio due to the large volatilization of bismuth element at high temperature leads to the performance deterioration of the sintered ceramic sample through structural analysis.
Claims (8)
1. A sodium bismuth titanate-based ceramic with stable dielectric properties at high temperature is characterized in that: the chemical composition is as follows: bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3，x=0.02、0.04，y=0.30。
2. Preparation of a compound of claim 1The method for preparing the bismuth sodium titanate-based ceramic with stable dielectric property at high temperature is characterized by comprising the following steps: according to Bi0.35Na0.65-0.5xRb0.5xTi0.7NbyO3，The stoichiometric ratio of x =0.02, 0.04 and y =0.30 is taken to prepare Bi2O3, Na2CO3, TiO2,Nb2O5, Rb2CO3Obtaining a mixture, performing first ball milling on the mixture to obtain slurry A, pre-sintering the slurry A to obtain pre-sintered powder, performing second ball milling on the pre-sintered powder to obtain slurry B, performing press molding on the slurry B to obtain a green body, and sintering the green body to obtain the sodium bismuth titanate-based ceramic with stable dielectric property;
the pre-burning program comprises the following steps: firstly heating to 800 ℃ and 850 ℃, preserving heat for 2-4h, then heating to 900 ℃ and 950 ℃, and preserving heat for 4-6 h.
3. The method for preparing the sodium bismuth titanate-based ceramic with stable dielectric properties at high temperature according to claim 2, wherein the method comprises the following steps: in the first ball milling process, the mass ratio of the alcohol to the zirconia balls to the raw materials is 0.6-0.8: 2.5-3: 1, the ball milling speed is 300-.
4. The method for preparing the sodium bismuth titanate-based ceramic with stable dielectric properties at high temperature according to claim 2, wherein the method comprises the following steps: in the second ball milling process, the mass ratio of the alcohol to the zirconia balls to the raw materials is 0.4-0.6: 2.5-3: 1, the ball milling speed is 300-.
5. The method for preparing the sodium bismuth titanate-based ceramic with stable dielectric properties at high temperature according to claim 2, wherein the method comprises the following steps: and (4) sieving the obtained slurry B with a 60-mesh sieve, taking undersize products, and pressing and forming.
6. The method for preparing a sodium bismuth titanate-based ceramic having stable dielectric properties at high temperatures according to claim 2 or 5, wherein: the pressure of the compression molding is 75-125MPa, and the pressure maintaining time is 1-2 min.
7. The method of claim 2, wherein the green body sintering procedure comprises: the sintering temperature is 1125-.
8. The use of the sodium bismuth titanate-based ceramic having stable dielectric properties at high temperatures according to claim 1 in a high temperature capacitor.
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