CN116425537B - Zr-doped strontium barium gadolinium niobate-zirconium dioxide composite ceramic material and preparation method thereof - Google Patents
Zr-doped strontium barium gadolinium niobate-zirconium dioxide composite ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 18
- -1 strontium barium gadolinium Chemical compound 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000003292 glue Substances 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- UCZXABKGSCALIN-UHFFFAOYSA-N [Gd+3].[O-2].[O-2].[Zr+4] Chemical compound [Gd+3].[O-2].[O-2].[Zr+4] UCZXABKGSCALIN-UHFFFAOYSA-N 0.000 claims description 5
- DKDQMLPMKQLBHQ-UHFFFAOYSA-N strontium;barium(2+);oxido(dioxo)niobium Chemical compound [Sr+2].[Ba+2].[O-][Nb](=O)=O.[O-][Nb](=O)=O.[O-][Nb](=O)=O.[O-][Nb](=O)=O DKDQMLPMKQLBHQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004146 energy storage Methods 0.000 abstract description 24
- 239000000919 ceramic Substances 0.000 abstract description 15
- 230000010287 polarization Effects 0.000 abstract description 13
- 230000005684 electric field Effects 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 230000005621 ferroelectricity Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
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- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a Zr-doped barium strontium gadolinium niobate-zirconium dioxide composite ceramic material, the structural formula of which is Sr 0.485 Ba 0.47 Gd 0.03 Nb 2‑x O 6‑δ ‑xZrO 2 The value of x is 0.01-0.3. The invention also discloses a preparation method of the composite ceramic material, which comprises the following steps: baCO is carried out 3 、SrCO 3 、Gd 2 O 3 、Nb 2 O 5 、ZrO 2 Fully mixing, ball milling, drying and presintering to obtain presintering powder; granulating the presintered powder under the action of a polyvinyl alcohol binder, keeping the presintered powder in a tabletting mode under cold isostatic pressing, discharging glue, and sintering. The invention is realized by that in Sr 0.485 Ba 0.47 Gd 0.03 Nb 2 O 6 Zr is introduced into a ceramic system 4+ The high breakdown electric field is obtained, the residual polarization is obviously reduced, the ferroelectricity gradually evolves from an original typical saturated loop to a slender electric hysteresis loop, and the energy storage density and the energy storage efficiency are obviously improved.
Description
Technical Field
The invention belongs to the technical field of ceramic material preparation, and particularly relates to a Zr-doped barium strontium niobate gadolinium-zirconium dioxide composite ceramic material and a preparation method of the ceramic material.
Background
The dielectric ceramic capacitor has the advantages of high power density, high charge and discharge speed, wide working temperature range and the like, and is widely used in the fields of pulse power sources, electronic circuits, electric automobiles and the like. However, the energy storage density of ceramic capacitors is too low, severely limiting their practical application.
NbO as tungsten bronze structure niobate material 6 Octahedron as basic structural unit has general structural formula (A1) 2 (A2) 4 C 4 (B1) 2 (B2) 8 O 30 . Different metal cations selectively occupy 5 non-equivalent crystallographic gap positions of A1, A2, B1, B2 and C sites according to the radius and valence state, and the filling condition of the crystallographic gap positions is regulated to enable the metal cations to generate various ferroelectric and relaxor ferroelectric materials with different phase transition temperatures and diffusion degrees, so that the metal cations become key materials for researching and developing lead-free electrostatic capacitors. However, the current research on tungsten bronze structure has focused mainly on full-filled tungsten bronze structure (Sr, na, bi) Nb 5 O 15 Ferroelectric, is used for explaining the influence of component and structure fluctuation on tungsten bronze ferroelectric and relaxation behavior, and in addition, the material system contains volatile Na/Bi element, so that sintering of densified ceramics is limited and integration in device application is influenced; in addition, the ceramic system not only has ferroelectric-paraelectric phase transformation, but also has ferroelectric-elastic phase transformation, and the complex phase transformation process leads to domain inversion and migration at high temperature to generate energy dissipation, so that breakdown field intensity is reduced, and the temperature stability characteristic of energy storage is limited; accordingly, in the face of the development of high integration and miniaturization of energy storage devices, there is an urgent need to seek and develop dielectric energy storage materials having high performance.
Sr having non-filled tungsten bronze structure 0.485 Ba 0.47 Gd 0.03 Nb 2 O 6 In the system, the A1 and A2 crystallographic positions of the system are selectively occupied by three ions of Sr, ba and Gd, and the degree of underfill of the crystal lattice is relative to Sr 0.53 Ba 0.47 Nb 2 O 6 The ions filled in the gaps are subjected to spontaneous displacement polarization along the direction of the c axis, so that the barium gadolinium strontium niobate shows higher dielectric constant, and the same asWhen saturated ferroelectric hysteresis loops are obtained (maximum polarization intensity up to 40. Mu.C/cm 2 ) However, its remnant polarization is 8.8. Mu.C/cm 2 The improvement of the recyclable energy storage density and the energy storage efficiency is not facilitated. Meanwhile, the ceramic is easy to generate abnormal growth of crystal grains and liquid phase melting areas during high-temperature sintering, so that the density is reduced to a great extent, and the electrical property and the energy storage property are damaged.
Disclosure of Invention
The invention aims to provide a Zr-doped barium strontium gadolinium niobate-zirconium dioxide composite ceramic material, which improves the energy storage density and the energy storage efficiency of the ceramic material.
The invention further aims to provide a preparation method of the Zr-doped barium strontium gadolinium niobate-zirconium dioxide composite ceramic material.
The technical proposal adopted by the invention is that the Zr-doped strontium barium gadolinium niobate-zirconium dioxide composite ceramic material has the structural formula of Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x O 6-δ -xZrO 2 The value of x is 0.01 to 0.3, preferably, the value of x is 0.2.
The preparation method of the Zr-doped barium strontium niobate gadolinium-zirconium dioxide composite ceramic material adopts another technical scheme, and is implemented according to the following steps:
step 1, according to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x O 6-δ -xZrO 2 Respectively weighing BaCO with the purity of more than 99.00 percent 3 、SrCO 3 、Gd 2 O 3 、Nb 2 O 5 、ZrO 2 Fully mixing, ball milling and drying to obtain a raw material mixture;
step 2, presintering the raw material mixture to obtain presintering powder;
and 3, granulating the presintered powder under the action of a polyvinyl alcohol binder, keeping the presintered powder in a tabletting mode under cold isostatic pressing, discharging glue, and sintering to obtain the Zr-doped strontium barium gadolinium niobate-zirconium dioxide composite ceramic material.
The present invention is also characterized in that,
in the step 2, the presintering temperature is 1000-1250 ℃ and the presintering time is 2-5 hours.
In the step 3, when the glue is discharged, the temperature is increased to 550 ℃ at 0.5 ℃/min for discharging the glue; the sintering temperature is 1300-1330 ℃, and the sintering time is 2-4 hours.
The beneficial effects of the invention are as follows: by adding a catalyst to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2 O 6 Zr is introduced into a ceramic system 4+ Directly obtaining the Zr-doped barium strontium gadolinium niobate-zirconium dioxide composite ceramic material; the material has a higher breakdown electric field, the residual polarization is obviously reduced, the ferroelectricity gradually evolves from an original typical saturated loop to an elongated electric hysteresis loop, and the energy storage density and the energy storage efficiency are obviously improved.
Drawings
FIG. 1 is a graph (one) of the micro-morphology of the ceramic material prepared in example 3;
FIG. 2 is a graph (II) of the micro morphology of the ceramic material prepared in example 3;
FIG. 3 is an XRD pattern of the ceramic material prepared in example 4;
FIG. 4 is a graph showing the dielectric spectrum of the ceramic material prepared in example 2 as a function of temperature at different test frequencies;
FIG. 5 is a complex impedance spectrum at 500℃of the ceramic materials prepared in examples 1 to 3;
FIG. 6 is a graph of hysteresis curves of the ceramic material prepared in comparative example 2 under different electric fields;
FIG. 7 is a graph of hysteresis curves of the ceramic material prepared in example 2 under different electric fields;
FIG. 8 is a graph showing the comparison of the maximum electric field strength that can be applied to the ceramic materials prepared in comparative examples 1 and 2 and examples 1 to 3;
FIG. 9 is a graph showing the recoverable energy storage density and energy storage efficiency of the ceramic materials prepared in comparative examples 1 and 2 and examples 1 to 3;
FIG. 10 is a graph of the Zr element energy spectrum in the ceramic material of the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The Zr-doped barium strontium gadolinium niobate-dioxideZirconium composite ceramic material with structural formula of Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x O 6-δ -xZrO 2 The value of x is 0.01-0.3;
preferably, x has a value of 0.2.
The invention relates to a preparation method of a Zr-doped barium strontium niobate gadolinium-zirconium dioxide composite ceramic material, which is implemented according to the following steps:
step 1, according to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x O 6-δ -xZrO 2 Respectively weighing BaCO with the purity of more than 99.00 percent 3 、SrCO 3 、Gd 2 O 3 、Nb 2 O 5 、ZrO 2 Fully mixing and ball milling for 10-18 hours, and drying for 12-24 hours at 60-70 ℃ to obtain a raw material mixture;
step 2, presintering the raw material mixture for 2-5 hours at the temperature of 1000-1250 ℃ to obtain presintering powder;
step 3, granulating the presintered powder under the action of a polyvinyl alcohol (PVA) binder, keeping the presintered powder for 1min under 200MPa cold isostatic pressing, then heating to 550 ℃ at 0.5 ℃/min for discharging glue, and sintering for 2-4 hours at 1300-1330 ℃ to obtain the Zr-doped strontium barium gadolinium niobate-zirconium dioxide composite ceramic material;
the invention uses non-equivalent Zr 4+ Introduced to replace Nb in the B position 5+ And induces relaxation, reduces remnant polarization, and simultaneously ZrO at grain boundaries 2 Higher electrical insulation properties, which are beneficial for improved energy storage properties, help to achieve the creation of interfacial polarization and to achieve a larger breakdown field.
The invention uses Zr 4+ Sr doped 0.485 Ba 0.47 Gd 0.03 Nb 2-x O 6-δ -xZrO 2 The composite ceramic system inhibits abnormal growth of anisometric grains of the tungsten bronze structure ceramic, forms compact ferroelectric energy storage material, reduces energy dissipation under an electric field and uniformly distributes ZrO at grain boundaries 2 The higher electrical insulation property leads the composite ceramic to have higher interface polarization and higher breakdown electricityA field; in addition, elements such as Bi, na, K and the like which are easy to volatilize in the high-temperature sintering process are not involved in the ceramic composition, the integration of devices is easy, the operation is simple, the requirements on equipment, manpower and sites are low, and the industrial production is expected to be realized.
Example 1
The invention relates to a preparation method of a Zr-doped barium strontium niobate gadolinium-zirconium dioxide composite ceramic material, which is implemented according to the following steps:
step 1, according to Sr 0.485 Ba 0.47 Gd 0.03 Nb 1.9 O 6-δ -0.1ZrO 2 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4851g BaCO with a purity of 99.00% 3 3.2191g of Gd with purity of 99.99% 2 O 3 0.1869g of Nb with purity of 99.90% 2 O 5 8.6855g of ZrO with a purity of 99.85% 2 0.4234g, putting into a nylon pot, using zirconium balls as grinding balls and absolute ethyl alcohol as ball milling media, ball milling for 16 hours with a ball mill at 400 rpm, drying for 15 hours at 80 ℃ in a drying oven, grinding for 30 minutes with a mortar, and sieving with a 80-mesh sieve to obtain a raw material mixture;
step 2, placing the raw material mixture into an alumina crucible, compacting by an agate rod to make the compacted density of the agate rod be 1.5g/cm 3 Capping, placing in a resistance furnace, heating to 1100 ℃ at a heating rate of 3 ℃/min for presintering for 4 hours, naturally cooling to room temperature, grinding for 10 minutes by using a mortar, and sieving by using a 120-mesh sieve to obtain presintering powder;
and 3, adding a polyvinyl alcohol aqueous solution with the mass fraction of 5% (the mass of the polyvinyl alcohol aqueous solution is 50% of the mass of the presintered powder) into the presintered powder, granulating, sieving with a 100-mesh sieve, preparing spherical particles, putting the spherical particles into a stainless steel die with the diameter of 15mm, pressing the spherical particles into a cylindrical blank with the thickness of 1.5mm under the pressure of 200MPa by using cold isostatic pressing, putting the cylindrical blank on a zirconia flat plate, putting the zirconia flat plate into an alumina closed sagger, heating the zirconia flat plate to 550 ℃ at the heating rate of 0.5 ℃/min, preserving heat for 2 hours, discharging glue, cooling to room temperature, heating to 1000 ℃ at the heating rate of 5 ℃/min, continuously heating to 1320 ℃ at the heating rate of 3 ℃/min, sintering for 2 hours, and naturally cooling to room temperature along with a furnace to obtain the SBN-Gd-Zr0.1 composite ceramic material.
Example 2
In step 1 of the present embodiment, the following Sr is used 0.485 Ba 0.47 Gd 0.03 Nb 1.8 O 6-δ -0.2ZrO 2 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4907g BaCO with a purity of 99.00% 3 3.2264g of Gd with purity of 99.99% 2 O 3 0.1873g of Nb with purity of 99.90% 2 O 5 8.2485g of ZrO with a purity of 99.85% 2 0.8488g, and the other steps were the same as in example 1 to obtain a SBN-Gd-Zr0.2 composite ceramic material.
Example 3
In step 1 of the present embodiment, the following Sr is used 0.485 Ba 0.47 Gd 0.03 Nb 1.7 O 6-δ -0.3ZrO 2 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4963g BaCO with a purity of 99.00% 3 3.2337g of Gd with purity of 99.99% 2 O 3 0.1877g of Nb with purity of 99.90% 2 O 5 7.8063g of ZrO with a purity of 99.85% 2 1.2760g, and the other steps were the same as in example 1 to obtain a SBN-Gd-Zr0.3 composite ceramic material.
Example 4
In step 1 of the present embodiment, the following Sr is used 0.485 Ba 0.47 Gd 0.03 Nb 1.99 O 6-δ -0.01ZrO 2 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4801g BaCO with a purity of 99.00% 3 3.2123g of Gd with purity of 99.99% 2 O 3 0.1865g of Nb with purity of 99.90% 2 O 5 9.0785g of ZrO with a purity of 99.85% 2 0.0423g, and the other steps were the same as those in example 1 to obtain SBN-Gd-Zr0.01 composite ceramic material.
Comparative example 1
According to Sr 0.53 Ba 0.47 Nb 2 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.7017g and purity of 9900% BaCO 3 3.2026g of Nb with purity of 99.90% 2 O 5 9.0956g, the other steps are the same as in example 1, to give Sr 0.53 Ba 0.47 Nb 2 O 6 A ceramic material.
Comparative example 2
According to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4795g BaCO with a purity of 99.00% 3 3.2119g of Gd with purity of 99.99% 2 O 3 0.1864g of Nb with purity of 99.90% 2 O 5 9.1221g, the other steps were the same as in example 1, to obtain a Gd-doped SBN tungsten bronze structure ferroelectric energy storage ceramic material (SBN-Gd 0.03).
The ceramic materials prepared in the above comparative examples 1 and 2 and examples 1 to 4 were subjected to a microscopic morphology test by using a Carle Zeiss GeminiSEM field emission scanning electron microscope, an XRD test by using a D/max-2200X-ray diffractometer, a dielectric property test by using an Agilent,4980A LCR meter, a ferroelectric property test by using a ferroelectric workstation and a connection temperature control device, and energy storage characteristics were evaluated, respectively. As can be seen from fig. 1 and 2, a dense ceramic sample can be obtained by this sintering method, and the introduction of Zr suppresses the growth of rod-like grains.
As can be seen from fig. 3, example 4 produced a ceramic material as a pure tetragonal tungsten bronze phase. As can be seen from FIG. 6, in comparative example 2, by adding Sr to the steel 0.53 Ba 0.47 Nb 2 O 6 Gd doped in the ceramic material increases the polarization intensity of the ceramic material, but the electric field intensity of the ceramic material is weaker; as shown in fig. 7 and 8, the present invention is implemented by using a method of adding a metal to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2 O 6 Incorporation of Zr into ceramic materials 4+ Not only the electric field strength of the ceramic material is enhanced, but also the residual polarization strength of the ceramic is remarkably reduced, and the electric hysteresis loop of the ceramic material is thinned relative to that of comparative example 2, the energy storage density and efficiency are as shown in figure 9, the energy storage performance is most excellent in example 2, and the breakdown field strength is 270kV cm -1 Maximum polarization intensity of 25.14. Mu.C.cm -2 A remnant polarization of 1.33. MuC·cm -2 The room temperature recoverable energy storage density is 2.67J cm -3 The efficiency was 91.21%.
The surfaces of the ceramic materials prepared in comparative examples 1, 2 and 1 to 4 are polished to a thickness of 0.5 to 0.6mm by using 320-mesh, 800-mesh and 1500-mesh sand paper in sequence, then silver paste with a thickness of 0.01 to 0.03mm is coated on the upper and lower surfaces of the ceramic, and the ceramic materials are placed in a resistance furnace for heat preservation for 30 minutes at 840 ℃. Ceramic electrical performance tests were performed using a HIOKI3532-50 and Agilent 4980A precision impedance analyzer, the results of which are shown in FIGS. 4 and 5. In comparison with the ceramic materials of comparative examples 1 and 2, the present invention is obtained by incorporating Zr into the ceramic material 4+ The relaxation of the ceramic is obviously enhanced, and when the value of x is 0.2, the dielectric constant of the material at room temperature is 1794.79 and the Curie temperature is 18.1 ℃.
FIG. 10 is a graph showing the energy spectrum of Zr in the ceramic material of the present invention, from which it can be found that the introduction of Zr occupies not only the crystallographic position of Nb in the tungsten bronze structure but also a part of Zr is represented by ZrO 2 The composite ceramic material is finally formed by the composition ceramic designed in a mode of equimolar ratio doping; notably the secondary phase ZrO of zirconium dioxide 2 The formation of (3) causes oxygen vacancies to form in barium strontium gadolinium niobate which theoretically promotes oxygen ion conduction, whereas ZrO with high resistivity is enriched at the grain boundary 2 Not only is favorable for blocking the conduction of oxygen ions, but also is favorable for increasing the intrinsic breakdown electric field of the material, so that Zr exists in two forms, and the energy storage performance of the material is more favorable for improving.
Zr prepared by the invention 4+ Sr doped 0.485 Ba 0.47 Gd 0.03 Nb 2-x O 6-δ -xZrO 2 Composite ceramic material, B site Zr 4+ Is introduced into induced polarization unit BO 6 The octahedron is distorted, the long-range distribution of ferroelectric domains is easy to break, nano polarized micro domains are formed, the relaxation is obviously enhanced, and the ZrO with high insulation is obtained 2 The distribution of the crystal grains at the grain boundary obviously improves the breakdown strength of the material, namely, high energy storage density and efficiency are realized.
Claims (1)
- The Zr-doped strontium barium gadolinium niobate-zirconium dioxide composite ceramic material is characterized in that the structural formula is Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x O 6-δ -xZrO 2 The value of x is 0.2; wherein Zr exists in two forms: (1) By Zr (Zr) 4+ The doped form occupies the crystallographic position of the tungsten bronze structure Nb, (2) in ZrO 2 The form of the grains is distributed at the grain boundaries;the preparation method of the Zr-doped barium strontium niobate gadolinium-zirconium dioxide composite ceramic material is implemented according to the following steps:step 1, according to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x O 6-δ -xZrO 2 Respectively weighing BaCO with the purity of more than 99.00 percent 3 、SrCO 3 、Gd 2 O 3 、Nb 2 O 5 、ZrO 2 Fully mixing, ball milling and drying to obtain a raw material mixture;step 2, presintering the raw material mixture to obtain presintering powder; the presintering temperature is 1000-1250 ℃, and the presintering time is 2-5 hours;step 3, granulating the presintered powder under the action of a polyvinyl alcohol binder, keeping the presintered powder in a tabletting mode under cold isostatic pressing, discharging glue, and sintering to obtain the Zr-doped strontium barium gadolinium niobate-zirconium dioxide composite ceramic material;during glue discharging, the temperature is increased to 550 ℃ at 0.5 ℃/min for glue discharging; the sintering temperature is 1300-1330 ℃, and the sintering time is 2-4 hours.
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