CN110204335B - Ceramic material with high energy storage density and efficiency and preparation method thereof - Google Patents
Ceramic material with high energy storage density and efficiency and preparation method thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 59
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 54
- 238000005498 polishing Methods 0.000 claims abstract description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052709 silver Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000005469 granulation Methods 0.000 claims abstract description 9
- 230000003179 granulation Effects 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 67
- 239000000919 ceramic Substances 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 44
- 239000011734 sodium Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 27
- 235000015895 biscuits Nutrition 0.000 claims description 21
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- 239000000203 mixture Substances 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 15
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 11
- 244000137852 Petrea volubilis Species 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 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 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 7
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 7
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- 229910003378 NaNbO3 Inorganic materials 0.000 description 6
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
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- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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Abstract
The invention discloses a ceramic material with high energy storage density and efficiency and a preparation method thereof, wherein the chemical formula of the ceramic material is (1-x) NaNbO3‑x(Bi0.5Na0.5)HfO3Wherein x is more than or equal to 0.05 and less than or equal to 0.2; the material is obtained by batching, ball milling, presintering, secondary ball milling, granulation molding, binder removal, sintering, polishing and silver coating electrode. The energy storage density calculated based on the electric hysteresis loop is 0.99-3.51J/cm3And the energy storage efficiency is between 60 and 80.1 percent. As a novel energy storage ceramic material, the material has the advantages of high energy storage density, simple preparation process, low cost, no pollution, easy large-scale production and the like, and has strong practicability.
Description
Technical Field
The invention relates to the technical field of dielectric energy storage ceramic materials, in particular to a sodium niobate-based ceramic material with high energy storage density and high energy storage efficiency and a preparation method thereof.
Background
In the later 70 s of the 20 th century, with the research and increasingly wide application of technologies such as nuclear physics, electron beams, accelerators, lasers, discharge theory, plasma and the like, pulse power technology is beginning to be widely applied in the fields of national defense, scientific experiments, industry and agriculture and medicine. Since the 21 st century, the pulse power technology and the high voltage new technology gradually become the emerging disciplines with high coverage rate and high technology integration of the current disciplines, and are one of the most active branch disciplines in the field of electrical engineering science. With the development of scientific technology, especially the needs of developed countries on national defense and space planning, the pulse power technology is gradually gaining attention. The pulse power technology is that the primary pulse waveform (millisecond to microsecond) required by the initial energy storage technology is generated, then the pulse shaping and switching technology is utilized, the pulse of the energy is compressed and shaped on the time scale, the amplification of the peak power of the output pulse is realized, the output pulse is output to a load, and a strong electric pulse power source is provided for a high-tech device and a new concept weapon. The main body of the pulse power device is a high-power pulse power supply which provides electromagnetic energy for a load of the pulse power device. Generally, the pulse power technology includes several links of initial energy source, intermediate energy storage, pulse compression and conversion, and load.
At present, the primary energy sources are mainly of the type electric (solid-state capacitors, supercapacitors, inductors, etc.), mechanical (motors, inertial energy storage) and chemical (lithium batteries, fuel cells). In which the solid state capacitor is at its high power density (-10)8W/kg), fast charge-discharge speed (nanosecond to microsecond) and long cycle life (50 ten thousand times) become energy storage modes preferred by pulse power technology, but the energy storage density (W) is higherrec) Is relatively low (10)-2-10-1Wh/kg), the requirements of integration, weight reduction and miniaturization of the pulse power device cannot be satisfied. At present, the methodThe capacitors applied in the high-power pulse power supply are mostly foil-structured capacitors and metallized film capacitors. The former has the problems of low energy storage density, easy fault explosion and the like; the latter has the disadvantages of short service life, small discharge current, etc. Therefore, in order to meet the requirements of special properties such as high energy storage density, long charging and discharging service life, large output current and the like of an energy storage element in a high-power pulse power supply, designing and preparing the high-performance energy storage dielectric material has important significance.
The dielectric materials currently used for solid state capacitors mainly include five major classes of polymers, ceramic-polymer composites, glass-ceramics and ceramics. Dielectric ceramics have moderate breakdown field strengths (E) relative to other energy storage dielectric materialsb) The energy storage capacitor has the advantages of low dielectric loss (tan delta), excellent temperature stability and anti-fatigue property, and can better meet the requirements of the fields of aerospace, oil drilling, electromagnetic pulse weapons and the like on the energy storage capacitor. Thus, ceramic dielectric materials are considered to be excellent materials for making high temperature resistant solid state capacitors. The prior lead-free energy storage ceramic material is mainly concentrated on BaTiO3、SrTiO3、(Bi0.5Na0.5)TiO3、(K0.5Na0.5)NbO3And AgNbO3And the like, however, it is difficult to achieve both high energy storage density and high energy storage efficiency with these materials. For example, Shen et al prepared 0.91BaTiO3-0.09BiYbO3The energy storage efficiency of the ceramic is up to 87 percent, but the energy storage density is only 0.71J/cm3(ii) a Preparation of AgNbO by Zhao et al3+0.1wt％MnO2Ceramics having an energy storage density of up to 2.5J/cm3However, the energy storage efficiency is only 56%, which limits their practical applications. Therefore, designing and preparing the lead-free energy storage dielectric ceramic with high energy storage density and high energy storage efficiency is a technical difficulty faced in the technical field of dielectric energy storage ceramic at present.
Disclosure of Invention
In view of the above problems, the present invention is directed to provide a ceramic material having both high energy storage density and efficiency, and a method for preparing the same, by doping (Bi)0.5Na0.5)HfO3In NaNbO3Polar nano micro areas are formed in the ceramic by induction, and low remanent polarization is obtained; the hybridization of the 6s of Bi and the 2p orbit of O is utilized to obtain high saturation polarization intensity; furthermore, (Bi)0.5Na0.5)HfO3The doping can obviously reduce NaNbO3The dielectric loss of the base ceramic improves the density, reduces the grain size, further improves the breakdown strength, and finally obtains the ceramic material with high energy storage density and high energy storage efficiency.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a ceramic material having both high energy storage density and efficiency, said ceramic material having a chemical composition of (1-x) NaNbO3-x(Bi0.5Na0.5)HfO3Wherein x is more than or equal to 0.05 and less than or equal to 0.2.
For the energy storage medium material, the following characteristics are necessary to obtain high energy storage density and energy storage efficiency: high saturation polarization, low remnant polarization and high breakdown strength.
Introduced by the invention of (Bi)0.5Na0.5)HfO3Has the following advantages:
(1)(Bi0.5Na0.5)HfO3hybridization of the 6s of middle Bi and the 2p orbital of O is beneficial to obtaining high saturation polarization.
(2) When introducing (Bi)0.5Na0.5)HfO3When (Bi)0.5Na0.5)2+And Hf4+Respectively enter into NaNbO3The A site and the B site of the ceramic break the long-range ordered structure of the ceramic, promote the formation of polar nanometer micro-regions and are beneficial to obtaining low residual polarization strength.
(3)Hf4+Relative to the same group of Ti4+The dielectric ceramic has better chemical stability, is beneficial to reducing dielectric loss and leakage current, and further obtains higher breakdown strength.
(4)(Bi0.5Na0.5)HfO3The introduction of (A) can promote NaNbO3The sintering of the ceramic obviously reduces the pore content and the grain size, thereby obtaining high breakdown strength.
A method for preparing a ceramic material with both high energy storage density and efficiency, comprising the steps of:
s1, calculating and weighing: drying analytically pure anhydrous sodium carbonate, niobium pentoxide, bismuth trioxide and hafnium dioxide raw materials for 10-15 hours at the temperature of 120 ℃ and 150 ℃, and then carrying out NaNbO treatment according to a chemical general formula (1-x)3-x(Bi0.5Na0.5)HfO3Sequentially weighing the raw materials according to the stoichiometric ratio in (x is more than or equal to 0.05 and less than or equal to 0.2), and sequentially pouring the raw materials into a ball milling tank to obtain a mixture;
s2, ball milling: the mixture obtained in step S1 is dissolved in ethanol to form ZrO2Ball milling for 12-20 hr with medium, stoving and sieving to obtain dry powder; the ratio of ethanol to mixture is 2: 1;
s3, pre-burning: pre-burning the dry powder obtained in the step S2 in air at 870-920 ℃ for 5-12 hours, and then grinding and sieving to obtain powder A;
s4, ball milling for multiple times: performing planetary ball milling on the powder A obtained in the step S3 in ethanol for 12-20 hours, drying, performing planetary ball milling on the powder in the ethanol for 12-20 hours, performing ball milling for multiple times in sequence, and finally drying to obtain powder B;
the ratio of ethanol to powder A is 2:1, the proportion just enables the ethanol to just immerse the powder, so that the ball-milled powder is more uniform, and the ball-milling effect can be improved;
s5, granulating and forming: adding the powder B obtained in the step S4 into polyvinyl alcohol according to 5% of the powder mass for granulation to obtain a formed biscuit;
s6, removing glue: placing the formed biscuit obtained in the step S5 in a medium temperature furnace, heating to 500-650 ℃, preserving heat for 2-5 hours, and naturally cooling along with the furnace;
s7, sintering: and (4) gradually heating the formed biscuit obtained in the step S6 to 1230-1310 ℃ by adopting a two-step heating method, preserving the heat for 1-5 hours, and naturally cooling along with the furnace to obtain the compact ceramic plate. 3. The method as claimed in claim 2, wherein the powder granulated in step S5 is dry-pressed under a pressure of 100-300 MPa.
Preferably, the rate of temperature rise in step S6 is specifically 1-3 deg.C/min.
Preferably, the two-step temperature raising method in step S7 is to raise the temperature to 600 ℃ at a temperature raising rate of 3-5 ℃/min, and then to raise the temperature to 1230-1310 ℃ at a temperature raising rate of 1-3 ℃/min.
Preferably, the polishing and silver-coated electrode is also included.
Preferably, the polishing and silver-impregnated electrode is obtained by polishing the ceramic sheet obtained in the step S7 to a thickness of 0.2-0.3mm, brushing silver paste on both sides by using a screen, heating and preserving heat, naturally cooling along with the furnace, and firing the silver-impregnated electrode.
Preferably, the specific operation process of grinding is as follows:
the two sides of the obtained ceramic wafer are firstly polished to be 1mm thick by 400-mesh water sand paper, then the two sides of the obtained ceramic wafer are polished to be 0.6mm thick by 600-mesh water sand paper, then the two sides of the obtained ceramic wafer are polished to be 0.35mm thick by 1500-mesh water sand paper, and finally the two sides of the obtained ceramic wafer are polished to be 0.2-0.3mm thick by diamond grinding paste;
subsequently, the polished sample was placed in an ultrasonic cleaner (KQ-300E type), cleaned with ethanol as a cleaning agent for 10 to 15min, and then placed in a forced air drying oven to be dried.
Preferably, the temperature is raised to 650-850 ℃ at a rate of 1-5 ℃/min, and the temperature is maintained for 0.5-1 hour.
Preferably, a testing step is also included.
Preferably, the test means that the crystal structure and the phase structure of the sample in the finished product are respectively tested by testing equipment, the microstructure evolution, the dielectric property and the electric hysteresis loop of the sample are observed, and the sample is placed in the silicone oil under the high-voltage test to prevent surface discharge.
The invention has the beneficial effects that:
the invention is realized by doping (Bi)0.5Na0.5)HfO3In NaNbO3Polar nano micro areas are formed in the ceramic by induction, and low remanent polarization is obtained; the hybridization of the 6s of Bi and the 2p orbit of O is utilized to obtain high saturation polarization intensity; furthermore, (Bi)0.5Na0.5)HfO3Can be significantly reducedLow NaNbO3The dielectric loss of the base ceramic improves the density of the base ceramic, reduces the grain size of the base ceramic, further improves the breakdown strength of the base ceramic, and finally obtains a ceramic material with high energy storage density and high energy storage efficiency;
the material is obtained by batching, ball milling, presintering, secondary ball milling, granulation molding, binder removal, sintering, polishing and silver coating electrode; the energy storage density calculated based on the electric hysteresis loop is 0.99-3.51J/cm3The energy storage efficiency is between 60 and 80.1 percent; the material is used as a novel energy storage ceramic material, has the advantages of high energy storage density, simple preparation process, low cost, no pollution, easy large-scale production and the like, and has strong practicability;
meanwhile, compared with the existing energy storage ceramic material, the ceramic material has the advantages of high energy storage density, simple preparation process, wide sintering temperature zone, low cost, no pollution, easy large-scale production and the like, and has strong practicability. Can be used as one of important energy storage candidate materials with excellent technical and economic aspects.
Drawings
FIG. 1(a) shows 0.95NaNbO in example 1 of the present invention3-0.05(Bi0.5Na0.5)HfO3An X-ray diffraction pattern of the ceramic at room temperature; FIG. 1(b) shows 0.95NaNbO in the example of the present invention3-0.05(Bi0.5Na0.5)HfO3Scanning electron micrographs of ceramics; FIG. 1(c) shows 0.95NaNbO in the example of the present invention3-0.05(Bi0.5Na0.5)HfO3Electrical hysteresis loop of ceramic.
FIG. 2(a) is 0.92NaNbO in example 2 of the present invention3-0.08(Bi0.5Na0.5)HfO3An X-ray diffraction pattern of the ceramic at room temperature; FIG. 2(b) is 0.92NaNbO in the example of the present invention3-0.08(Bi0.5Na0.5)HfO3Scanning electron micrographs of ceramics; FIG. 2(c) is 0.92NaNbO in the example of the present invention3-0.08(Bi0.5Na0.5)HfO3Electrical hysteresis loop of ceramic.
FIG. 3(a) is 0.89NaNbO in example 3 of the present invention3-0.11(Bi0.5Na0.5)HfO3An X-ray diffraction pattern of the ceramic at room temperature; FIG. 3(b) is 0.89NaNbO in the example of the present invention3-0.11(Bi0.5Na0.5)HfO3Scanning electron micrographs of ceramics; FIG. 3(c) is 0.89NaNbO in the example of the present invention3-0.11(Bi0.5Na0.5)HfO3Electrical hysteresis loop of ceramic.
FIG. 4(a) is 0.85NaNbO in example 4 of the present invention3-0.15(Bi0.5Na0.5)HfO3An X-ray diffraction pattern of the ceramic at room temperature; FIG. 4(b) is 0.85NaNbO in the example of the present invention3-0.15(Bi0.5Na0.5)HfO3Scanning electron micrographs of ceramics; FIG. 4(c) is 0.85NaNbO in the example of the present invention3-0.15(Bi0.5Na0.5)HfO3Electrical hysteresis loop of ceramic.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following further description is made with reference to the accompanying drawings and examples, it should be understood that the specific examples described herein are only for the purpose of explaining the present invention, and are not intended to limit the present invention.
Example 1
S1, calculating and weighing: drying analytically pure anhydrous sodium carbonate, niobium pentoxide, bismuth trioxide and hafnium dioxide raw materials at 120 ℃ for 15 hours, and then carrying out treatment according to the chemical formula of 0.95NaNbO3-0.05(Bi0.5Na0.5)HfO3Weighing the raw materials according to the stoichiometric ratio, and pouring the raw materials into a ball milling tank to obtain a mixture;
s2, ball milling: the mixture obtained in step S1 is dissolved in ethanol to form ZrO2Ball milling for 12 hours in a planetary way by taking balls as a medium, drying and sieving to obtain dry powder;
s3, pre-burning: pre-burning the dry powder obtained in the step S2 in air at 920 ℃ for 5 hours, and then grinding and sieving to obtain powder A;
s4, ball milling for multiple times: performing planetary ball milling on the powder A obtained in the step S3 in ethanol for 12 hours, drying, performing planetary ball milling on the powder in the ethanol for 12 hours, performing ball milling for 3 times in sequence, and finally drying to obtain powder B;
s5, granulating and forming: adding polyvinyl alcohol into the powder B obtained in the step S4 according to 5% of the mass of the powder for granulation, and performing dry pressing molding on the granulated powder under the pressure of 100MPa to obtain a molded biscuit;
s6, removing glue: placing the formed biscuit obtained in the step S5 in a medium temperature furnace, heating to 650 ℃ at the heating rate of 3 ℃/min, preserving heat for 2 hours, and naturally cooling along with the furnace;
s7, sintering: heating the formed biscuit obtained in the step S6 to 600 ℃ at the heating rate of 5 ℃/min, heating to 1310 ℃ at the heating rate of 3 ℃/min, preserving heat for 2.5 hours, and naturally cooling along with the furnace to obtain a compact ceramic plate;
s8, polishing and silver-coated electrode: polishing the ceramic plate obtained in the step S7 to a thickness of 0.3mm, specifically: the two sides of the obtained ceramic wafer are firstly polished to be 1mm thick by 400-mesh water sand paper, then the two sides of the obtained ceramic wafer are polished to be 0.6mm thick by 600-mesh water sand paper, then the two sides of the obtained ceramic wafer are polished to be 0.35mm thick by 1500-mesh water sand paper, and finally the two sides of the obtained ceramic wafer are polished to be 0.2-0.3mm thick by diamond grinding paste; in order to improve the final screen printing quality of a product, the polishing step is improved, the conventional polishing mode for directly polishing the required thickness is improved into a step-by-step polishing mode, and particularly, a step-by-step polishing mode of a four-step method is adopted, so that compared with the direct polishing mode, the method has the advantages that: the grinding precision is high, the surface is smooth, the polishing precision is high, and the screen printing is favorably and better carried out; the breakdown electric field of the material is improved;
then, the polished sample is placed in an ultrasonic cleaner (KQ-300E type), ethanol is used as a cleaning agent, the sample is cleaned for 10-15min, and then the sample is placed in a blast drying oven to be dried;
brushing silver paste on both sides by using a screen, heating to 650 ℃ at the heating rate of 5 ℃/min, preserving heat for 0.5 hour, naturally cooling along with the furnace, and sintering the silver-infiltrated electrode to obtain a finished product.
The crystal structure and phase structure of the pre-sintered powder and the ceramic sample were determined using an X-ray diffraction analyzer (XRD), and the microstructure evolution of the ceramic sample was observed using a Scanning Electron Microscope (SEM). The dielectric properties were tested with an agilent E4980A precision LCR tester. The ferroelectric analyzer TF-2000 is adopted to test the electric hysteresis loop of the ceramic and glass ceramic samples. For high-voltage testing, the samples were placed in silicone oil to prevent surface discharges.
TABLE I shows the results of the property tests of the ceramic material of example 1
Example 2
S1, calculating and weighing: drying analytically pure anhydrous sodium carbonate, niobium pentoxide, bismuth trioxide and hafnium dioxide raw materials at 140 ℃ for 13 hours, and then carrying out treatment according to the chemical formula of 0.92NaNbO3-0.08(Bi0.5Na0.5)HfO3Weighing the raw materials according to the stoichiometric ratio, and pouring the raw materials into a ball milling tank to obtain a mixture;
s2, ball milling: the mixture obtained in step S1 is dissolved in ethanol to form ZrO2Ball milling for 15 hours in a planetary way by taking the ball as a medium, drying and sieving to obtain dry powder;
s3, pre-burning: pre-burning the dry powder obtained in the step S2 in air at 900 ℃ for 8 hours, and then grinding and sieving to obtain powder A;
s4, ball milling for multiple times: performing planetary ball milling on the powder A obtained in the step S3 in ethanol for 15 hours, drying, performing planetary ball milling on the powder in the ethanol for 20 hours, performing ball milling for 2 times in sequence, and finally drying to obtain powder B;
s5, granulating and forming: adding the powder B obtained in the step S4 into polyvinyl alcohol according to 5 percent of the mass of the powder for granulation, and performing dry pressing molding on the granulated powder under the pressure of 150MPa to obtain a molded biscuit
S6, removing glue: placing the formed biscuit obtained in the step S5 in a medium temperature furnace, heating to 600 ℃ at the heating rate of 2 ℃/min, preserving heat for 3 hours, and naturally cooling along with the furnace;
s7, sintering: heating the formed biscuit obtained in the step S6 to 600 ℃ at the heating rate of 4 ℃/min, heating to 1280 ℃ at the heating rate of 2 ℃/min, preserving heat for 3 hours, and naturally cooling along with the furnace to obtain a compact ceramic plate;
s8, polishing and silver-coated electrode: polishing the ceramic wafer obtained in the step S7 to the thickness of 0.25mm, wherein the specific polishing steps are the same as those in example 1, after silver paste is brushed on the two sides by using a silk screen, the temperature is increased to 700 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 0.5 hour, the ceramic wafer is naturally cooled along with a furnace, and the silver infiltrated electrode is fired to obtain a finished product.
The test method was the same as in example 1
Table II shows the results of the property tests of the ceramic material of example 2
Example 3
S1, calculating and weighing: drying analytically pure anhydrous sodium carbonate, niobium pentoxide, bismuth trioxide and hafnium dioxide raw materials at 150 ℃ for 10 hours, and then carrying out NaNbO treatment according to the chemical formula of 0.893-0.11(Bi0.5Na0.5)HfO3Weighing the raw materials according to the stoichiometric ratio, and pouring the raw materials into a ball milling tank to obtain a mixture;
s2, ball milling: the mixture obtained in step S1 is dissolved in ethanol to form ZrO2Ball milling for 20 hours in a planetary way by taking the balls as a medium, drying and sieving to obtain dry powder;
s3, pre-burning: pre-burning the dry powder obtained in the step S2 in air at 890 ℃ for 10 hours, and then grinding and sieving to obtain powder A;
s4, ball milling for multiple times: performing planetary ball milling on the powder A obtained in the step S3 in ethanol for 15 hours, drying, performing planetary ball milling on the powder in the ethanol for 12 hours, performing ball milling for 3 times in sequence, and finally drying to obtain powder B;
s5, granulating and forming: adding polyvinyl alcohol into the powder B obtained in the step S4 according to 5% of the mass of the powder for granulation, and performing dry pressing molding on the granulated powder under the pressure of 300MPa to obtain a molded biscuit;
s6, removing glue: placing the formed biscuit obtained in the step S5 in a medium temperature furnace, heating to 500 ℃ at the heating rate of 1 ℃/min, preserving heat for 5 hours, and naturally cooling along with the furnace;
s7, sintering: heating the formed biscuit obtained in the step S6 to 600 ℃ at the heating rate of 3 ℃/min, heating to 1260 ℃ at the heating rate of 1 ℃/min, preserving the heat for 5 hours, and naturally cooling along with the furnace to obtain a compact ceramic plate;
s8, polishing and silver-coated electrode: polishing the ceramic wafer obtained in the step S7 to the thickness of 0.2mm, wherein the specific polishing steps are the same as those in example 1, after silver paste is brushed on the two sides by using a silk screen, the temperature is raised to 650 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 1 hour, then the ceramic wafer is naturally cooled along with a furnace, and the silver infiltrated electrode is fired to obtain a finished product.
The test method was the same as in example 1
TABLE III shows the results of the performance tests of the ceramic material of example 3
Example 4
S1, calculating and weighing: drying analytically pure anhydrous sodium carbonate, niobium pentoxide, bismuth trioxide and hafnium dioxide raw materials at 130 ℃ for 14 hours, and then carrying out NaNbO treatment according to the chemical formula of 0.853-0.15(Bi0.5Na0.5)HfO3Weighing the raw materials according to the stoichiometric ratio, and pouring the raw materials into a ball milling tank to obtain a mixture;
s2, ball milling: the mixture obtained in step S1 is dissolved in ethanol to form ZrO2Ball milling for 15 hours in a planetary way by taking the ball as a medium, drying and sieving to obtain dry powder;
s3, pre-burning: pre-burning the dry powder obtained in the step S2 in air at 900 ℃ for 6 hours, and then grinding and sieving to obtain powder A;
s4, ball milling for multiple times: carrying out planetary ball milling on the powder A obtained in the step S3 in ethanol for 18 hours, drying, carrying out planetary ball milling on the powder in the ethanol for 18 hours, carrying out ball milling for 3 times in sequence, and finally drying to obtain powder B;
s5, granulating and forming: adding polyvinyl alcohol into the powder B obtained in the step S4 according to 5% of the mass of the powder for granulation, and performing dry pressing molding on the granulated powder under the pressure of 250MPa to obtain a molded biscuit;
s6, removing glue: placing the formed biscuit obtained in the step S5 in a medium temperature furnace, heating to 620 ℃ at the heating rate of 2 ℃/min, preserving heat for 3 hours, and naturally cooling along with the furnace;
s7, sintering: heating the formed biscuit obtained in the step S6 to 600 ℃ at the heating rate of 4 ℃/min, heating to 1255 ℃ at the heating rate of 3 ℃/min, preserving the heat for 2 hours, and naturally cooling along with the furnace to obtain a compact ceramic plate;
s8, polishing and silver-coated electrode: polishing the ceramic wafer obtained in the step S47 to the thickness of 0.2mm, wherein the specific polishing steps are the same as those in example 1, after silver paste is brushed on the two sides by using a silk screen, the temperature is increased to 800 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 0.5 hour, the ceramic wafer is naturally cooled along with a furnace, and the silver infiltrated electrode is fired to obtain a finished product.
The test method was the same as in example 1
TABLE IV shows the results of the property tests of the ceramic material of example 4
Example 5
S1, calculating and weighing: drying analytically pure anhydrous sodium carbonate, niobium pentoxide, bismuth trioxide and hafnium dioxide raw materials at 135 ℃ for 12 hours, and then carrying out NaNbO treatment according to the chemical formula of 0.803-0.20(Bi0.5Na0.5)HfO3Weighing the raw materials according to the stoichiometric ratio, and pouring the raw materials into a ball milling tank to obtain a mixture;
s2, ball milling: the mixture obtained in step S1 is dissolved in ethanol to form ZrO2Ball milling is carried out for 17 hours in a planetary way by taking the ball as a medium, and the dry powder is obtained after drying and sieving;
s3, pre-burning: pre-burning the dry powder obtained in the step S2 in air at 870 ℃ for 12 hours, and then grinding and sieving to obtain powder A;
s4, ball milling for multiple times: carrying out planetary ball milling on the powder A obtained in the step S3 in ethanol for 16 hours, drying, carrying out planetary ball milling on the powder in the ethanol for 16 hours, carrying out ball milling for 2 times in sequence, and finally drying to obtain powder B;
s5, granulating and forming: adding polyvinyl alcohol into the powder B obtained in the step S4 according to 5% of the mass of the powder for granulation, and performing dry pressing molding on the granulated powder under the pressure of 200MPa to obtain a molded biscuit;
s6, removing glue: placing the formed biscuit obtained in the step S5 in a medium temperature furnace, heating to 580 ℃ at the heating rate of 2.5 ℃/min, preserving the temperature for 4 hours, and naturally cooling along with the furnace;
s7, sintering: heating the formed biscuit obtained in the step S6 to 600 ℃ at the heating rate of 3.5 ℃/min, heating to 1230 ℃ at the heating rate of 2 ℃/min, preserving the heat for 4 hours, and naturally cooling along with the furnace to obtain a compact ceramic plate;
s8, polishing and silver-coated electrode: polishing the ceramic wafer obtained in the step S57 to the thickness of 0.3mm, wherein the specific polishing steps are the same as those in example 1, after silver paste is brushed on the two sides by using a silk screen, the temperature is increased to 800 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 0.5 hour, the ceramic wafer is naturally cooled along with a furnace, and the silver infiltrated electrode is fired to obtain a finished product.
The test method was the same as in example 1
TABLE V shows the results of the property tests of the ceramic material of example 5
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A ceramic material having both high energy storage density and efficiency, characterized by: the chemical composition of the ceramic material is (1-x) NaNbO3-x(Bi0.5Na0.5)HfO3Wherein x is more than or equal to 0.05 and less than or equal to 0.2;
the preparation method of the ceramic material comprises the following steps:
S1、calculating and weighing: drying analytically pure anhydrous sodium carbonate, niobium pentoxide, bismuth trioxide and hafnium dioxide raw materials for 10-15 hours at the temperature of 120 ℃ and 150 ℃, and then carrying out NaNbO treatment according to a chemical general formula (1-x)3-x(Bi0.5Na0.5)HfO3Sequentially weighing the raw materials according to the stoichiometric ratio in (x is more than or equal to 0.05 and less than or equal to 0.2), and sequentially pouring the raw materials into a ball milling tank to obtain a mixture;
s2, ball milling: the mixture obtained in step S1 is dissolved in ethanol to form ZrO2Ball milling for 12-20 hr with medium, stoving and sieving to obtain dry powder;
s3, pre-burning: pre-burning the dry powder obtained in the step S2 in air at 870-920 ℃ for 5-12 hours, and then grinding and sieving to obtain powder A;
s4, ball milling for multiple times: carrying out planetary ball milling on the powder A obtained in the step S3 in ethanol for 12-20 hours;
after drying, performing planetary ball milling on the powder in ethanol for 12-20 hours, performing ball milling for multiple times in sequence, and finally drying to obtain powder B;
s5, granulating and forming: adding the powder B obtained in the step S4 into polyvinyl alcohol according to 5% of the powder mass for granulation to obtain a formed biscuit;
s6, removing glue: placing the formed biscuit obtained in the step S5 in a medium temperature furnace, heating to 500-650 ℃, preserving heat for 2-5 hours, and naturally cooling along with the furnace;
s7, sintering: and (4) gradually heating the formed biscuit obtained in the step S6 to 1230-1310 ℃ by adopting a two-step heating method, preserving the heat for 1-5 hours, and naturally cooling along with the furnace to obtain the compact ceramic plate.
2. The ceramic material with high energy storage density and efficiency as claimed in claim 1, wherein the powder granulated in step S5 is dry-pressed under a pressure of 100MPa to 300 MPa.
3. Ceramic material with both high energy storage density and efficiency according to claim 1, characterized in that the rate of temperature rise in step S6 is in particular 1-3 ℃/min.
4. The ceramic material with high energy storage density and efficiency as claimed in claim 1, wherein the two-step temperature raising method in step S7 is to raise the temperature to 600 ℃ at a temperature raising rate of 3-5 ℃/min, and then raise the temperature to 1230-1310 ℃ at a temperature raising rate of 1-3 ℃/min.
5. The ceramic material with high energy storage density and efficiency as claimed in claim 1, further comprising polished and silver electrodes.
6. The ceramic material with high energy storage density and efficiency as claimed in claim 5, wherein the polished and silver-impregnated electrode is obtained by polishing the ceramic sheet obtained in step S7 to a thickness of 0.2-0.3mm, brushing silver paste on both sides with a screen, heating and maintaining the temperature, naturally cooling along with a furnace, and sintering the silver-impregnated electrode.
7. The ceramic material with high energy storage density and efficiency as claimed in claim 6, wherein the specific operation process of grinding is as follows:
the two sides of the obtained ceramic wafer are firstly polished to be 1mm thick by 400-mesh water sand paper, then the two sides of the obtained ceramic wafer are polished to be 0.6mm thick by 600-mesh water sand paper, then the two sides of the obtained ceramic wafer are polished to be 0.35mm thick by 1500-mesh water sand paper, and finally the two sides of the obtained ceramic wafer are polished to be 0.2-0.3mm thick by diamond grinding paste;
subsequently, the polished sample was placed in an ultrasonic cleaner (KQ-300E type), cleaned with ethanol as a cleaning agent for 10 to 15min, and then placed in a forced air drying oven to be dried.
8. The ceramic material with high energy storage density and efficiency as claimed in claim 7, wherein the temperature is raised to 650-850 ℃ at a rate of 1-5 ℃/min, and the temperature is maintained for 0.5-1 hour.
9. The ceramic material with high energy storage density and efficiency as claimed in any one of claims 1-8, wherein the preparation method further comprises a testing step, wherein the testing step comprises testing the crystal structure and phase structure of the sample in the finished product by a testing device respectively, observing the microstructure evolution, dielectric property and electric hysteresis loop of the sample, and placing the sample in silicone oil under high-voltage test to prevent surface discharge.
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| CN112266246B (en) * | 2020-11-02 | 2023-04-11 | 华北理工大学 | Method for preparing Hf, bi and Ca co-doped potassium-sodium niobate lead-free piezoelectric ceramic by solid-phase sintering method |
| CN113582685B (en) * | 2021-08-05 | 2022-07-15 | 湖南省美程陶瓷科技有限公司 | Lead-free piezoelectric ceramic material for breathing machine and preparation method thereof |
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