CN113788673A - Titanium dioxide-based ceramic material with medium-low frequency, ultralow dielectric loss and high dielectric constant and preparation method thereof - Google Patents
Titanium dioxide-based ceramic material with medium-low frequency, ultralow dielectric loss and high dielectric constant and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 58
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012856 weighed raw material Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- 239000003985 ceramic capacitor Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910002966 CaCu3Ti4O12 Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a titanium dioxide-based ceramic material with medium-low frequency, ultralow dielectric loss and high dielectric constant and a preparation method thereof, wherein the general formula of the ceramic material is (Cu)1/3Nb2/3)xTi1‑xO2Wherein x represents a mole fraction, and the value of x is 0.005-0.015. The preparation method of the ceramic material is simple, low in cost, good in repeatability and high in yield, and the metal element Cu is doped in the titanium dioxide-based ceramic material2+And Nb5+The ceramic material is made to have a frequency of 40-106The dielectric ceramic material has high dielectric constant and low dielectric loss within the Hz range, particularly remarkably reduces the medium and low frequency dielectric loss of the ceramic material, and is 40-104Dielectric loss in Hz frequency range is always kept below 0.03 and dielectric constantThe number is high, the frequency and the temperature stability are always kept above 26000, the frequency and the temperature stability are kept between-7.5% and 7.5%, the parameter requirements of the X9F ceramic capacitor are met, and the ceramic capacitor has great application value.
Description
Technical Field
The invention belongs to the technical field of giant dielectric ceramic materials, and particularly relates to a titanium dioxide-based ceramic material with medium and low frequency, ultralow dielectric loss, high dielectric constant, high frequency stability and high temperature stability and a preparation method thereof.
Background
With the increasing demand of human beings for energy, the requirements for energy storage devices are also higher and higher, and in order to meet the requirements of electronic components for development towards miniaturization, high performance and the like, dielectric materials have become high-tech functional materials which are widely researched in recent years. Increasing the dielectric constant of dielectric materials is a direct and effective way to obtain capacitors with high energy storage performance, and giant dielectric materials have been widely studied because of their ultra-high dielectric constant. The giant dielectric material mainly comprises ferroelectric and CaCu3Ti4O12(CCTO)、TiO2Base ceramics, and the like. The ferroelectric material is difficult to apply to practice due to the phase transition temperature of the ferroelectric material appearing at room temperature, and the metal element lead also has great influence on the environment, so that the ferroelectric material is difficult to continuously use; the CCTO material has no phase change, and the dielectric constant is stable in the temperature range of 100-600K, so people pay attention to the CCTO material, and ACu is derived and researched3Ti4O12A material. And ACu3Ti4O12Although ceramic (abbreviated as ACTO, A ═ Ca, Y, La, Cd, etc.) has a high dielectric constant, the dielectric loss is too large, and this problem affects its application in the production of multilayer ceramic capacitors (MLCC). TiO compared to other dielectric ceramics2The base ceramic has the advantages of environmental friendliness, good frequency stability and low dielectric loss, but the high frequency stability and the high temperature stability are ensured, and the high dielectric constant and the medium-low frequency ultralow dielectric loss are still difficult.
In recent years, the research on the titanium dioxide-based ceramic material co-doped with pentavalent and hexavalent titanium is insufficient, but most of the titanium dioxide-based ceramic materials have relatively high dielectric constants which only reach about 10000, and meanwhile, the high-frequency stability and the high-temperature stability are difficult to ensure, the low-frequency and ultralow dielectric loss is rare, the relatively low dielectric loss can only reach about 0.08, and the requirement of practical application cannot be met.
Disclosure of Invention
The invention aims to provide a titanium dioxide-based ceramic material which has the advantages of medium-low frequency, ultralow dielectric loss, high dielectric constant, high frequency stability, high thermal stability, strong practicability and easy production, and provides a preparation method for the ceramic material, which has the advantages of simple process, good repeatability and low cost.
In view of the above object, the titanium dioxide-based ceramic material used in the present invention has the general formula (Cu)1/3Nb2/3)xTi1-xO2Wherein x represents a mole fraction, the value of x is 0.005-0.015, and the value of x is preferably 0.005.
The preparation method of the titanium dioxide-based ceramic material comprises the following steps:
1. according to (Cu)1/3Nb2/3)xTi1-xO2Respectively weighing CuO and Nb with the purity of more than 99.5 percent according to the stoichiometric ratio2O5、TiO2Uniformly mixing all the weighed raw materials, putting the mixture into a nylon tank, fully mixing and ball-milling the mixture for 20 to 24 hours by taking zirconium dioxide balls as grinding balls and absolute ethyl alcohol as a ball-milling medium, and drying the mixture for 12 to 24 hours at 80 to 100 ℃ to obtain a raw material mixture.
2. And pre-sintering the raw material mixture at 1000-1100 ℃ for 2-4 hours to obtain pre-sintered powder.
3. And granulating, tabletting and removing the glue from the pre-sintered powder, and sintering for 8-15 hours at 1350-1450 ℃ in an air atmosphere to obtain the titanium dioxide-based ceramic material.
In the step 2, the raw material mixture is preferably heated to 1100 ℃ at a heating rate of 3 ℃/min, and then pre-fired at a constant temperature for 3 hours.
In the step 3, the pre-sintered powder is preferably subjected to granulation, tabletting and binder removal, and then sintered for 10 hours at 1390-1430 ℃ under the air atmosphere and closed conditions.
In the step 3, the tabletting is performed by using a powder tabletting machine to maintain the pressure for 3-4 minutes under the pressure of 6MPa, and the cylindrical blank is pressed.
The invention has the following beneficial effects:
1. the invention introduces the metal element Cu into the titanium dioxide ceramic material2+And Nb5+The ceramic material has medium and low frequency, ultra-low dielectric loss (< 0.08) and high dielectric constant (> 2.1 × 10)4) In the case of (3), both high frequency stability and high thermal stability are achieved. Under the condition of 1kHz meeting practical application conditions, the dielectric constant is as high as 27100, and the dielectric loss is only 0.012. Meanwhile, the dielectric constant is kept about 25000 and the dielectric loss is lower than 0.08 within the temperature range of-200 to 200 ℃. In the temperature range of-55 to 200 ℃ (Cu)1/3Nb2/3)0.005Ti0.995O2The capacitance change rate of the ceramic material is kept between-4.9 percent and 7.0 percent at 1kHz, between-7.2 percent and 3.2 percent at 10kHz, between-7.5 percent and 1.1 percent at 50kHz and between-4.9 percent and 3.1 percent at 100kHz, thereby meeting the application requirement range of X9F (+ -7.5 percent) ceramic capacitors.
2. The ceramic material has the advantages of simple preparation method, good repeatability, high yield, strong practicability and easy production. The raw materials selected by the invention do not contain heavy metals such as lead and the like, and are environment-friendly.
Drawings
FIG. 1 is an XRD pattern of the ceramic material prepared in examples 1 to 3.
FIG. 2 is a graph showing the relationship between the dielectric constant and the dielectric loss of the ceramic material prepared in examples 1 to 3 and the frequency of the test.
FIG. 3 is a graph of the dielectric constant and dielectric loss as a function of test temperature for the ceramic material prepared in example 1 at different frequencies.
FIG. 4 is a graph of the rate of change of capacitance at different frequencies versus test temperature for the ceramic material prepared in example 1.
FIG. 5 is a graph showing the changes of dielectric constant and dielectric loss with the test temperature at various frequencies of the ceramic material prepared in example 1 at an ultra-low temperature.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. According to (Cu)1/3Nb2/3)0.005Ti0.995O2Respectively weighing 0.0496g of CuO (purity 99.7%) and Nb according to the stoichiometric ratio of (A)2O5(purity 99.9%) 0.1653g TiO2(purity 99.5%) 29.7851g, mixing all the weighed raw materials uniformly, putting the mixture into a nylon pot, ball-milling the mixture for 24 hours at 401 rpm by using a ball mill with zirconium dioxide balls as grinding balls and absolute ethyl alcohol as a ball-milling medium, wherein the mass ratio of the absolute ethyl alcohol to all the raw materials is 1:1.2, separating the zirconium balls, drying the zirconium balls for 24 hours at 80 ℃, and grinding the zirconium balls for 30 minutes by using a mortar to obtain a raw material mixture.
2. Placing the raw material mixture in an alumina crucible, covering, heating to 1100 ℃ at the heating rate of 3 ℃/min, presintering at constant temperature for 3 hours, naturally cooling to room temperature, and discharging to obtain the presintering powder.
3. Grinding the pre-sintered powder for 30 minutes by using a mortar, adding a polyvinyl alcohol aqueous solution with the mass fraction of 5 percent into the pre-sintered powder, wherein the adding amount of the polyvinyl alcohol aqueous solution is 50 percent of the mass of the pre-sintered powder, granulating, sieving by using a 120-mesh sieve to prepare spherical particles, putting the spherical particles into a stainless steel die with the diameter of 11.5mm, maintaining the pressure for 3-4 minutes by using a powder tablet press under the pressure of 6MPa, and pressing the spherical particles into a cylindrical blank with the thickness of 1.5 mm; placing the cylindrical blank on a zirconia flat plate, placing the zirconia flat plate in an alumina porcelain boat, heating to 500 ℃ in a muffle furnace within 380 minutes, preserving heat for 2 hours, naturally cooling to room temperature along with the furnace, heating to 1000 ℃ within 100 minutes under the air atmosphere in a tubular furnace, heating to 1390 ℃ at the heating rate of 2 ℃/minute, preserving heat for 10 hours, and naturally cooling to room temperature along with the furnace to obtain the titanium dioxide-based ceramic material.
Example 2
In step 1 of this example, the following (Cu)1/3Nb2/3)0.01Ti0.99O2In the stoichiometric ratio of (A), 0.0989g of CuO (purity: 99.7%) was weighed out,Nb2O5(purity 99.9%) 0.3298g TiO2(purity 99.5%) 29.5712g, and step 3, the temperature was raised to 1000 ℃ in 100 minutes, then to 1410 ℃ at a rate of 2 ℃/minute in the air atmosphere in the tube furnace, and the temperature was maintained for 10 hours, and the other steps were the same as in example 1, to obtain a titania-based ceramic material.
Example 3
In step 1 of this example, the following (Cu)1/3Nb2/3)0.015Ti0.985O20.1481g of CuO (purity 99.7%) and Nb were weighed in the stoichiometric ratio of (1)2O5(purity 99.9%) 0.4938g TiO2(purity 99.5%) 29.3581g, and in step 3, the temperature was raised to 1000 ℃ in 100 minutes, then to 1430 ℃ in 2 ℃/minute in the air atmosphere in the tube furnace, and the temperature was maintained for 10 hours, and the other steps were the same as in example 1, to obtain a titanium dioxide-based ceramic material.
XRD tests were carried out on the ceramic materials prepared in examples 1 to 3 using a D/max-2200X-ray diffractometer (manufactured by Japan chemical Co., Ltd.), respectively, and the results are shown in FIG. 1. As can be seen from FIG. 1, the ceramic materials prepared in examples 1 to 3 are all pure rutile phase structures, and no second phase is generated.
And (3) sequentially polishing the surface of the ceramic material prepared in the embodiment 1-3 by using 1000-mesh, 1500-mesh and 2000-mesh sand papers to a thickness of 0.5-0.6 mm, cleaning the ceramic material after ultrasonic treatment, then respectively coating silver pastes with the thickness of 0.01-0.03 mm on the upper surface and the lower surface of the ceramic material, placing the ceramic material in a muffle furnace for heat preservation at 840 ℃ for 30 minutes, and naturally cooling the ceramic material to room temperature. Respectively performing characterization test on the dielectric properties of the ceramics by using a Cuilient4294A type precision impedance analyzer and an E4980A type LCR tester manufactured by Agilent technologies, and calculating the dielectric constant epsilon according to the following formular：
εr＝4Ct/(πε0d)
In the formula: c is capacitance, t is thickness of ceramic plate, epsilon0The results are shown in FIGS. 2-3 for the vacuum dielectric constant and d for the diameter of the ceramic wafer.
As can be seen from FIG. 2, when the test frequency is 1kHz, the ceramic materials prepared in examples 1-3 have dielectric constants of 27100, 41200 and 78500 in sequence, and dielectric losses of 0.012, 0.033 and 0.067 in sequence; the dielectric loss of the ceramic material prepared in the embodiment 1 is always kept below 0.08 in a frequency test range, and particularly, when the ceramic material is at a middle and low frequency which has practical application significance, the dielectric loss is always kept below 0.03 while the high dielectric constant is kept above 26000, so that the requirement of the ceramic material for the middle and low frequency ultralow loss is met. As can be seen from FIG. 3, the ceramic material prepared in example 1 has a dielectric constant of about 25000 and a dielectric loss of less than 0.08 at a temperature of-175 ℃.
To further demonstrate the thermal stability of the ceramic materials produced, the rate of change of capacitance of the ceramic materials was calculated as shown in FIG. 4. As can be seen from the figure, the ceramic material prepared in the example 1 has the capacitance change rate of-4.9% -7.0% at 1kHz, of-7.2% -3.2% at 10kHz, of-7.5% -1.1% at 50kHz and of-4.9% -3.1% at 100kHz in the temperature range of-55 to 200 ℃, and both satisfy the application requirement range (+/-7.5%) of the X9F ceramic capacitor.
In order to further prove that the prepared ceramic material has excellent temperature stability and frequency stability, the dielectric constant and the dielectric loss of the ceramic material at the ultralow temperature under each frequency of 0.1-1000 kHz are researched, as shown in FIG. 5. As can be seen from the figure, the ceramic material prepared in example 1 has dielectric constant of above 20000 and dielectric loss of below 0.08 in the temperature range of 60-300K and the test frequency range of 0.1-1000 kHz.
Therefore, the ceramic material disclosed by the invention has the advantages of medium-low frequency ultralow dielectric loss, high dielectric constant, high frequency stability and high temperature stability, and meets the application requirements of an X9F ceramic capacitor. The ceramic material has excellent medium and low frequency dielectric property and stronger practicability. Therefore, the method is expected to be applied to electronic markets such as MLCC.
Claims (6)
1. A titanium dioxide-based ceramic material with medium-low frequency, ultralow dielectric loss and high dielectric constant is characterized in that: the ceramic material has the general formula of (Cu)1/3Nb2/3)xTi1-xO2And the value of x is 0.005-0.015.
2. The titanium dioxide-based ceramic material according to claim 1, wherein: the value of x is 0.005.
3. A method for preparing the titanium dioxide-based ceramic material with low and medium frequency, ultralow dielectric loss and high dielectric constant as claimed in claim 1, which is characterized by comprising the following steps:
(1) according to (Cu)1/3Nb2/3)xTi1-xO2Respectively weighing CuO and Nb with the purity of more than 99.5 percent according to the stoichiometric ratio2O5、TiO2Uniformly mixing all the weighed raw materials, putting the mixture into a nylon tank, fully mixing and ball-milling the mixture for 20 to 24 hours by taking zirconium dioxide balls as grinding balls and absolute ethyl alcohol as a ball-milling medium, and drying the mixture for 12 to 24 hours at 80 to 100 ℃ to obtain a raw material mixture;
(2) pre-burning the raw material mixture at 1000-1100 ℃ for 2-4 hours to obtain pre-burned powder;
(3) and granulating, tabletting and degumming the pre-sintered powder, and sintering for 8-15 hours at 1350-1450 ℃ in an air atmosphere under a closed condition to obtain the titanium dioxide-based ceramic material.
4. The method for preparing the titanium dioxide-based ceramic material with low and medium frequency, ultralow dielectric loss and high dielectric constant according to claim 3, wherein the method comprises the following steps: in the step (2), the raw material mixture is heated to 1100 ℃ at the heating rate of 3 ℃/minute, and is presintered for 3 hours at constant temperature.
5. The method for preparing the titanium dioxide-based ceramic material with low and medium frequency, ultralow dielectric loss and high dielectric constant according to claim 3, wherein the method comprises the following steps: and (3) granulating, tabletting and degumming the pre-sintered powder, and sintering at 1390-1430 ℃ for 10 hours under the air atmosphere condition.
6. The method for preparing the titanium dioxide-based ceramic material with low and medium frequency, ultralow dielectric loss and high dielectric constant according to claim 3, wherein the method comprises the following steps: and (3) performing pressure maintaining for 3-4 minutes by using a powder tablet machine under the pressure of 6MPa, and pressing into a cylindrical blank.
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