CN117024141A - Composite ion modified sodium bismuth titanate-based energy storage ceramic material and preparation method thereof - Google Patents
Composite ion modified sodium bismuth titanate-based energy storage ceramic material and preparation method thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 45
- -1 ion modified sodium bismuth Chemical class 0.000 title claims abstract description 40
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 109
- 150000002500 ions Chemical class 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 36
- 238000000227 grinding Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 28
- 238000000498 ball milling Methods 0.000 claims description 25
- 238000003746 solid phase reaction Methods 0.000 claims description 25
- 238000005245 sintering Methods 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052573 porcelain Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 4
- 238000000462 isostatic pressing Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 16
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 abstract description 12
- 229910003237 Na0.5Bi0.5TiO3 Inorganic materials 0.000 abstract description 4
- 229910002367 SrTiO Inorganic materials 0.000 abstract description 3
- 230000005684 electric field Effects 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052797 bismuth Inorganic materials 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000004570 mortar (masonry) Substances 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 230000010287 polarization Effects 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- SYJBLFMEUQWNFD-UHFFFAOYSA-N magnesium strontium Chemical compound [Mg].[Sr] SYJBLFMEUQWNFD-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 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
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
The invention is suitable for the technical field of sodium bismuth titanate-based energy storage ceramic materials, and provides a composite ion modified sodium bismuth titanate-based energy storage ceramic material, wherein the general formula of the material is (Na 0.5 Bi 0.5 ) 1‑y Sr y Ti 1‑ x M x O 3 X is more than or equal to 0.05 and less than or equal to 0.20,0.20, y is more than or equal to 0.30; and M is a composite ion with an average valence of 4. The invention also provides a preparation method of the composite ion modified bismuth sodium titanate-based energy storage ceramic material. The invention uses SrTiO 3 ‑MO 2 Introduction of Na 0.5 Bi 0.5 TiO 3 In the method, sr element enters into A site of perovskite structure to compensate metal ion vacancy caused by volatilization of Bi and Na, and composite ion M enters into B site to replace 4-valent Ti, thereby effectively inhibiting oxygen vacancy,the random electric field of the B site of the perovskite structure is enhanced, the breakdown strength of the ceramic is improved, the hysteresis characteristic of an electric hysteresis loop is reduced, and the energy storage efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of sodium bismuth titanate-based energy storage ceramic materials, and particularly relates to a composite ion modified sodium bismuth titanate-based energy storage ceramic material and a preparation method thereof.
Background
The dielectric material is a key core material for manufacturing the capacitor, has the function of storing charges, and is widely applied to electronic circuits to realize the functions of coupling, filtering, decoupling, high-frequency vibration absorption, resonance, bypass, neutralization, timing, integration, differentiation, compensation, bootstrap, frequency division and the like. The properties of the dielectric material directly determine the quality of the capacitor element. With the development trend of miniaturization and high integration of electronic products, capacitors face technical challenges of microminiaturization, ultra-large capacity and ultra-thin type, and higher requirements are put on dielectric breakdown strength, energy storage efficiency and energy storage density of dielectric materials. Ferroelectric materials have high spontaneous polarization but because of low breakdown strength, the hysteresis of polarization with electric field is large, resulting in lower energy storage density and efficiency. Therefore, the development of ferroelectric energy storage materials with low polarization hysteresis and high breakdown strength has very important practical significance.
Bismuth sodium titanate (Na) 0.5 Bi 0.5 TiO 3) Is a relaxation ferroelectric with perovskite structure having higher Curie point, and its spontaneous polarization intensity can be up to 70 μC/cm 2 However, bi and Na at the A-position are volatile elements, in pure Na 0.5 Bi 0.5 TiO 3 The material is easy to generate chemical defects such as vacancies and the like in synthesis, so that the leakage conduction loss is larger, the breakdown strength is lower, and the advantage of high spontaneous polarization strength is difficult to be exerted. By directing to Na 0.5 Bi 0.5 TiO 3 And a proper amount of other components are added to form a solid solution, so that the leakage conduction loss can be reduced, and the breakdown strength can be improved. For example, chinese patent No. CN112341192B discloses a sodium bismuth titanate-based lead-free dielectric material with high energy storage density and a preparation method thereof, which utilizes SrTi 0.9 (Cu 1/3 Nb 2/3 ) 0.1 O 3 -Bi 0.5 K 0.5 TiO 3 The breakdown strength of the modified sodium bismuth titanate-based energy storage ceramic reaches 220kV/cm, the efficiency reaches 76%, and the effective energy storage density reaches 2.04J/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the CN111978082B modified sodium bismuth titanate based energy storage ceramic material doped with strontium magnesium niobate and preparation method thereof discloses use of Sr (Mg) 1/3 Nb 2/3 )O 3 Modified sodium bismuth titanate-based energy storage ceramic with breakdown strength up to 140kV/cm, efficiency up to 52%, and effective energy storage density up to 1.59J/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the CN111393161B bismuth sodium titanate strontium titanate based energy storage ceramic material and preparation method thereof disclose the use of SrTiO 3- BaBi 2 Nb 2 O 9 The breakdown strength of the modified sodium bismuth titanate-based energy storage ceramic reaches 250kV/cm, the efficiency reaches 86%, and the effective energy storage density reaches 3.09J/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the sodium bismuth titanate-based electronic ceramic with high energy storage density and high efficiency of CN111217604B discloses the use of BaTiO 3- Sr(Sc 0.5 Nb 0.5 )O 3 The breakdown strength of the modified sodium bismuth titanate-based energy storage ceramic reaches 185kV/cm, the efficiency reaches 83%, and the effective energy storage density reaches 1.83J/cm 3 。
However, in terms of development requirements, the puncture resistance and energy storage effect of the existing doped modified sodium bismuth titanate-based energy storage ceramic are still low, and the miniaturization requirement of electronic products is difficult to meet, so that the development of the energy storage ceramic with better performance has important significance.
Disclosure of Invention
The embodiment of the invention aims to provide a composite ion modified sodium bismuth titanate-based energy storage ceramic material, which aims to solve the problems in the background technology.
The embodiment of the invention is realized in such a way that the composite ion modified sodium bismuth titanate-based energy storage ceramic material has the general formula (Na 0.5 Bi 0.5 ) 1-y Sr y Ti 1-x M x O 3 Wherein x is more than or equal to 0.05 and less than or equal to 0.20,0.20, y is more than or equal to 0.30;
wherein M is a complex ion (Sn 1/2 Hf 1/2 ) 4+ 、(Zr 1/3 Sn 1/3 Hf 1/3 ) 4+ 、(Al 1/3 Hf 1/3 Ta 1/3 ) 4+ 、(Mg 1/5 Al 1/5 Ta 3/5 ) 4+ One of them.
Another object of the embodiment of the invention is to provide a preparation method of the composite ion modified sodium bismuth titanate based energy storage ceramic material, which comprises the following steps:
(1) And (3) batching: carbonic acid is added intoSodium, bismuth oxide, titanium oxide, strontium carbonate, and M oxide according to the chemical formula (Na 0.5 Bi 0.5 ) 1- y Sr y Ti 1-x M x O 3 Mixing the mixture in a molar ratio of x being more than or equal to 0.05 and less than or equal to 0.20,0.20 and y being more than or equal to 0.30 to obtain a mixture;
(2) Mixing: adding absolute ethyl alcohol into the mixture, continuously ball milling, and uniformly mixing to form slurry;
(3) And (3) drying: drying the slurry at constant temperature to remove ethanol, and grinding to obtain uniformly mixed powder;
(4) Solid phase reaction: placing the powder in a mould, pressing and forming for 3-5 min under 150-200 MPa, placing the formed lump material in a solid-phase reaction furnace, preserving heat for 3-5 h at 850-1000 ℃ and carrying out solid-phase reaction;
(5) Ball milling: grinding the lump materials after the solid phase reaction to obtain ceramic powder, adding absolute ethyl alcohol into the ceramic powder, and continuously ball-milling to uniformly mix the powder to form ceramic slurry;
(6) And (3) drying: drying the ceramic slurry at constant temperature to remove ethanol, and grinding to obtain uniformly mixed ceramic powder;
(7) Granulating and forming: sieving ceramic powder, adding PVA solution, molding under 150-200 MPa, grinding, sieving to mix PVA with ceramic powder to obtain powder particles, placing the powder particles in a grinding tool, molding under 150-200 MPa, and isostatic pressing under 200-300 MPa to form ceramic green compact;
(8) And (3) glue discharging: preserving the heat of the ceramic green body, and discharging PVA in the ceramic green body to obtain a ceramic green body;
(9) Sintering: sintering the porcelain blank, and cooling to obtain the composite ion modified bismuth sodium titanate-based energy storage ceramic material.
Preferably, in the step (2), the addition amount of the absolute ethyl alcohol is 0.5-2 times of the mass of the mixture, and the ball milling time is 1-3 hours.
Preferably, in the step (5), the addition amount of the absolute ethyl alcohol is 0.5-2 times of the mass of the ceramic powder, and the ball milling time is 6-8 hours.
Preferably, in step (7), the mass concentration of the PVA solution is 3%.
Preferably, in the step (8), the temperature of the heat preservation is 500 ℃, and the time of the heat preservation is 0.5-1 h.
Preferably, in the step (9), the sintering temperature is 1000-1200 ℃, and the sintering time is 2-3 h.
The SrTiO is prepared from the composite ion modified bismuth sodium titanate based energy storage ceramic material 3 -MO 2 (M is a composite ion (Sn) having an average valence of 4 1/2 Hf 1/2 ) 4+ 、(Zr 1/3 Sn 1/3 Hf 1/3 ) 4+ 、(Al 1/3 Hf 1/3 Ta 1/3 ) 4+ And (Mg) 1/5 Al 1/5 Ta 3/5 ) 4+ ) Introduction of Na 0.5 Bi 0.5 TiO 3 In which a compound having the chemical formula (Na) is prepared by a solid phase reaction and sintering method 0.5 Bi 0.5 ) 1-y Sr y Ti 1-x M x O 3 Wherein x and y represent mole fraction, x ranges from 0.05 to 0.20, y ranges from 0.20 to 0.30, sr element enters A site of perovskite structure to compensate metal ion vacancy caused by volatilization of Bi and Na, and composite ion M enters B site to replace 4-valent Ti, thereby effectively inhibiting oxygen vacancy, enhancing random electric field of B site of perovskite structure, improving breakdown strength of ceramic, reducing hysteresis characteristic of electric hysteresis loop, improving energy storage efficiency, and the breakdown strength of the energy storage ceramic material prepared by the embodiment of the invention can reach 330kV/cm, and the effective energy storage density can reach 4.41J/cm 3 The energy storage efficiency reaches 77 percent.
Drawings
Fig. 1 is an SEM image of a composite ion modified sodium bismuth titanate based energy storage ceramic material provided in embodiment 1 of the present invention;
FIG. 2 is an XRD spectrum of a composite ion modified sodium bismuth titanate based energy storage ceramic material provided in example 1 of the present invention;
FIG. 3 is a graph showing the dielectric constant and dielectric loss of the composite ion modified sodium bismuth titanate based energy storage ceramic material according to the embodiment 1 of the present invention;
FIG. 4 is a graph showing the results of the hysteresis loop and energy storage properties of the composite ion modified bismuth sodium titanate based energy storage ceramic material provided in example 1 of the present invention;
fig. 5 is an SEM image of a composite ion modified sodium bismuth titanate based energy storage ceramic material provided in example 2 of the present invention;
FIG. 6 is an XRD pattern of a composite ion modified sodium bismuth titanate based energy storage ceramic material provided in example 2 of the present invention;
FIG. 7 is a graph showing the dielectric constant and dielectric loss of the composite ion modified sodium bismuth titanate based energy storage ceramic material according to the embodiment 2 of the present invention;
FIG. 8 is a graph showing the results of the hysteresis loop and energy storage properties of the composite ion modified bismuth sodium titanate based energy storage ceramic material provided in example 2 of the present invention;
fig. 9 is an SEM image of a composite ion modified sodium bismuth titanate based energy storage ceramic material provided in example 3 of the present invention;
FIG. 10 is an XRD pattern of a composite ion modified sodium bismuth titanate based energy storage ceramic material provided in example 3 of the present invention;
FIG. 11 is a graph showing the dielectric constant and dielectric loss of the composite ion modified sodium bismuth titanate based energy storage ceramic material according to the embodiment 3 of the present invention;
FIG. 12 is a graph showing the results of the hysteresis loop and energy storage properties of the composite ion modified bismuth sodium titanate based energy storage ceramic material provided in example 3 of the present invention;
fig. 13 is an SEM image of a composite ion modified sodium bismuth titanate based energy storage ceramic material provided in example 4 of the present invention;
FIG. 14 is an XRD pattern of a composite ion modified sodium bismuth titanate based energy storage ceramic material provided in example 4 of the present invention;
FIG. 15 is a graph showing the dielectric constant and dielectric loss of the composite ion modified sodium bismuth titanate based energy storage ceramic material according to example 4 of the present invention;
FIG. 16 is a graph showing the results of the hysteresis loop and energy storage properties of the composite ion modified bismuth sodium titanate based energy storage ceramic material provided in example 4 of the present invention;
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The preparation method of the composite ion modified sodium bismuth titanate-based energy storage ceramic material comprises the following steps:
(1) And (3) batching: sodium carbonate, bismuth oxide, titanium oxide, strontium carbonate, and M oxide (M is a compound ion (Sn) having an average valence of 4 1/2 Hf 1/2 ) 4+ 、(Zr 1/3 Sn 1/3 Hf 1/3 ) 4+ 、(Al 1/3 Hf 1/3 Ta 1/3 ) 4+ And (Mg) 1/5 Al 1/5 Ta 3/5 ) 4+ ) According to the chemical formula (Na) 0.5 Bi 0.5 ) 1-y Sr y Ti 1-x M x O 3 The molar ratio of x is in the range of 0.05 to 0.20 and y is in the range of 0.20 to 0.30 to obtain a mixture;
(2) Mixing: adding 0.5-2 times of absolute ethyl alcohol into the mixture, and continuously ball milling for 1-3 hours to uniformly mix the powder to form slurry;
(3) And (3) drying: drying the slurry in an oven at a constant temperature of 80 ℃, removing ethanol, and grinding by using a mortar to obtain uniformly mixed powder;
(4) Solid phase reaction: placing the uniformly mixed powder into a mould to be pressed and molded for 3-5 min under 150-200 MPa, placing the molded lump material into a solid phase reaction furnace to be subjected to solid phase reaction at 850-1000 ℃ for 3-5 h;
(5) Ball milling: grinding the lump materials subjected to the solid-phase reaction in a mortar to obtain ceramic powder, adding 0.5-2 times of absolute ethyl alcohol into the obtained ceramic powder, and continuously ball-milling for 6-8 hours to uniformly mix the powder to form ceramic slurry;
(6) And (3) drying: placing the ceramic slurry in an oven at 80 ℃ for constant temperature drying, removing ethanol, and grinding by using a mortar to obtain uniformly mixed ceramic powder;
(7) Granulating and forming: sieving ceramic powder with a 150-mesh sieve, adding a PVA solution with the mass concentration of 3%, molding under 150-200 MPa, grinding, sieving with a 150-mesh sieve to uniformly mix PVA in the ceramic powder to obtain powder particles, placing the powder particles in a grinding tool, compacting under the pressure of 150-200 MPa, and performing isostatic compaction under the pressure of 200-300 MPa to form a ceramic green body;
(8) And (3) glue discharging: preserving heat for 0.5-1 h at 500 ℃, and discharging PVA in the ceramic green body to obtain a ceramic green body;
(9) Sintering: and (3) preserving the temperature of the porcelain blank at 1000-1200 ℃ for 2-3 hours, sintering, and cooling.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
Example 1
According with chemical composition (Na 0.5 Bi 0.5 ) 0.75 Sr 0.25 Ti 0.88 (Sn 1/2 Hf 1/2 ) 0.12 O 3 The preparation method of the energy storage ceramic material comprises the following steps:
(1) And (3) batching: sodium carbonate, bismuth oxide, titanium oxide, strontium carbonate, tin oxide and hafnium oxide are mixed according to the chemical formula (Na 0.5 Bi 0.5 ) 0.75 Sr 0.25 Ti 0.88 (Sn 1/2 Hf 1/2 ) 0.12 O 3 Is mixed according to the mole ratio of the components to obtain a mixture;
(2) Mixing: adding absolute ethyl alcohol with the mass 1.5 times to the mixture, and continuously ball-milling for 1h to uniformly mix the powder to form slurry;
(3) And (3) drying: drying the slurry in an oven at a constant temperature of 80 ℃, removing ethanol, and grinding by using a mortar to obtain uniformly mixed powder;
(4) Solid phase reaction: placing the uniformly mixed powder into a die, pressing and forming for 3min under 150MPa, placing the formed block into a solid-phase reaction furnace, and preserving the temperature for 3h at 900 ℃ to perform solid-phase reaction;
(5) Ball milling: grinding the solid-phase reacted material block in a mortar to obtain ceramic powder, adding absolute ethyl alcohol with the mass 1.5 times that of the obtained ceramic powder, and continuously ball-milling for 8 hours to uniformly mix the powder to form slurry;
(6) And (3) drying: drying the slurry in an oven at the constant temperature of 80 ℃, removing ethanol, and grinding by using a mortar to obtain uniformly mixed ceramic powder;
(7) Granulating and forming: sieving the ceramic powder with a 150-mesh sieve, adding PVA solution with the mass concentration of 3%, forming under 200MPa, grinding, and sieving with the 150-mesh sieve to uniformly mix PVA in the ceramic powder; placing powder particles into a grinding tool, pressing and forming under the pressure of 200MPa, and then performing isostatic pressing under the pressure of 250MPa to form a ceramic green body;
(8) And (3) glue discharging: preserving the temperature at 500 ℃ for 30min, and discharging PVA in the ceramic green body to obtain a porcelain body;
(9) Sintering: and (3) preserving the temperature of the porcelain blank for 2 hours at 1150-1200 ℃ for sintering, and cooling to obtain the composite ion modified sodium bismuth titanate-based energy storage ceramic sheet.
Example 2
According with chemical composition (Na 0.5 Bi 0.5 ) 0.75 Sr 0.25 Ti 0.88 (Zr 1/3 Sn 1/3 Hf 1/3 ) 0.12 O 3 The preparation method of the energy storage ceramic material comprises the following steps:
(1) And (3) batching: sodium carbonate, bismuth oxide, titanium oxide, strontium carbonate, zirconium oxide, tin oxide, hafnium oxide, and a catalyst of the formula (Na 0.5 Bi 0.5 ) 0.75 Sr 0.25 Ti 0.88 (Zr 1/3 Sn 1/3 Hf 1/3 ) 0.12 O 3 Is mixed according to the mole ratio of the components to obtain a mixture;
(2) Mixing: adding absolute ethyl alcohol with the mass 1.5 times to the mixture, and continuously ball-milling for 1h to uniformly mix the powder to form slurry;
(3) And (3) drying: drying the slurry in an oven at a constant temperature of 80 ℃, removing ethanol, and grinding by using a mortar to obtain uniformly mixed powder;
(4) Solid phase reaction: placing the uniformly mixed powder into a die, pressing and forming for 3min under 150MPa, placing the formed block into a solid-phase reaction furnace, and preserving the temperature for 3h at 900 ℃ to perform solid-phase reaction;
(5) Ball milling: grinding the solid-phase reacted material block in a mortar to obtain ceramic powder, adding absolute ethyl alcohol with the mass 1.5 times that of the obtained ceramic powder, and continuously ball-milling for 8 hours to uniformly mix the powder to form slurry;
(6) And (3) drying: drying the slurry in an oven at the constant temperature of 80 ℃, removing ethanol, and grinding by using a mortar to obtain uniformly mixed ceramic powder;
(7) Granulating and forming: sieving ceramic powder with a 150-mesh sieve, adding a PVA solution with the mass concentration of 3%, molding under 200MPa, grinding, sieving with a 150-mesh sieve to ensure that PVA is uniformly mixed in the ceramic powder, placing powder particles in a grinding tool, compacting under the pressure of 200MPa, and then compacting under the pressure of 250MPa, thereby forming a ceramic green body;
(8) And (3) glue discharging: preserving the temperature at 500 ℃ for 30min, and discharging PVA in the ceramic green body to obtain a porcelain body;
(9) Sintering: and (3) preserving the temperature of the porcelain blank for 2 hours at 1150-1200 ℃ for sintering, and cooling to obtain the composite ion modified sodium bismuth titanate-based energy storage ceramic sheet.
Example 3
According with chemical composition (Na 0.5 Bi 0.5 ) 0.75 Sr 0.25 Ti 0.88 (Al 1/3 Hf 1/3 Ta 1/3 ) 0.12 O 3 The preparation method of the energy storage ceramic material comprises the following steps:
(1) And (3) batching: sodium carbonate, bismuth oxide, titanium oxide, strontium carbonate, aluminum oxide, hafnium oxide and tantalum oxide are mixed according to the chemical formula (Na 0.5 Bi 0.5 ) 0.75 Sr 0.25 Ti 0.88 (Al 1/3 Hf 1/3 Ta 1/3 ) 0.12 O 3 Is mixed according to the mole ratio of the components to obtain a mixture;
(2) Mixing: adding absolute ethyl alcohol with the mass 1.5 times to the mixture, and continuously ball-milling for 1h to uniformly mix the powder to form slurry;
(3) And (3) drying: drying the slurry in an oven at a constant temperature of 80 ℃, removing ethanol, and grinding by using a mortar to obtain uniformly mixed powder;
(4) Solid phase reaction: placing the uniformly mixed powder into a die, pressing and forming for 3min under 150MPa, placing the formed block into a solid-phase reaction furnace, and preserving the temperature for 3h at 900 ℃ to perform solid-phase reaction;
(5) Ball milling: grinding the solid-phase reacted material block in a mortar to obtain ceramic powder, adding absolute ethyl alcohol with the mass 1.5 times that of the obtained ceramic powder, and continuously ball-milling for 8 hours to uniformly mix the powder to form slurry;
(6) And (3) drying: drying the slurry in an oven at the constant temperature of 80 ℃, removing ethanol, and grinding by using a mortar to obtain uniformly mixed ceramic powder;
(7) Granulating and forming: sieving ceramic powder with a 150-mesh sieve, adding a PVA solution with the mass concentration of 3%, molding under 200MPa, grinding, sieving with a 150-mesh sieve to ensure that PVA is uniformly mixed in the ceramic powder, placing powder particles in a grinding tool, compacting under the pressure of 200MPa, and then compacting under the pressure of 250MPa, thereby forming a ceramic green body;
(8) And (3) glue discharging: preserving the temperature at 500 ℃ for 30min, and discharging PVA in the ceramic green body to obtain a porcelain body;
(9) Sintering: and (3) preserving the temperature of the porcelain blank for 2 hours at 1150-1200 ℃ for sintering, and cooling to obtain the composite ion modified sodium bismuth titanate-based energy storage ceramic sheet.
Example 4
According with chemical composition (Na 0.5 Bi 0.5 ) 0.75 Sr 0.25 Ti 0.88 ((Mg 1/5 Al 1/5 Ta 3/5 ) 0.12 O 3 The preparation method of the energy storage ceramic material comprises the following steps:
(1) And (3) batching: sodium carbonate, bismuth oxide, titanium oxide, strontium carbonate, magnesium oxide, aluminum oxide and tantalum oxide are mixed according to the chemical formula (Na 0.5 Bi 0.5 ) 0.75 Sr 0.25 Ti 0.88 ((Mg 1/5 Al 1/5 Ta 3/5 ) 0.12 O 3 Is mixed according to the mole ratio of the components to obtain a mixture;
(2) Mixing: adding absolute ethyl alcohol with the mass 1.5 times to the mixture, and continuously ball-milling for 1h to uniformly mix the powder to form slurry;
(3) And (3) drying: drying the slurry in an oven at a constant temperature of 80 ℃, removing ethanol, and grinding by using a mortar to obtain uniformly mixed powder;
(4) Solid phase reaction: placing the uniformly mixed powder into a die, pressing and forming for 3min under 150MPa, placing the formed block into a solid-phase reaction furnace, and preserving the temperature for 3h at 900 ℃ to perform solid-phase reaction;
(5) Ball milling: grinding the solid-phase reacted material block in a mortar to obtain ceramic powder, adding absolute ethyl alcohol with the mass 1.5 times that of the obtained ceramic powder, and continuously ball-milling for 8 hours to uniformly mix the powder to form slurry;
(6) And (3) drying: drying the slurry in an oven at the constant temperature of 80 ℃, removing ethanol, and grinding by using a mortar to obtain uniformly mixed ceramic powder;
(7) Granulating and forming: sieving ceramic powder with a 150-mesh sieve, adding a PVA solution with the mass concentration of 3%, molding under 200MPa, grinding, sieving with a 150-mesh sieve to ensure that PVA is uniformly mixed in the ceramic powder, placing powder particles in a grinding tool, compacting under the pressure of 200MPa, and then compacting under the pressure of 250MPa, thereby forming a ceramic green body;
(8) And (3) glue discharging: preserving the temperature at 500 ℃ for 30min, and discharging PVA in the ceramic green body to obtain a porcelain body;
(9) Sintering: and (3) preserving the temperature of the porcelain blank for 2 hours at 1150-1200 ℃ for sintering, and cooling to obtain the composite ion modified sodium bismuth titanate-based energy storage ceramic sheet.
Performance test:
the ceramic wafer prepared in example 1 is analyzed by SEM to obtain microscopic morphology, the characterization of which is shown in figure 1, and according to figure 1, the average size of the ceramic crystal grains is about 2.6 mu m, and the ceramic wafer is compact and has no obvious pores; the XRD pattern of the ceramic sheet was analyzed by X-ray diffractometer and shown in FIG. 2, and as can be seen from FIG. 2, sr 2+ Ion sum (Sn) 1/2 Hf 1/2 ) 4+ The composite ions enter perovskite lattices to form a single stable perovskite structure solid solution ceramic phase; for ceramicsThe sheet is subjected to analysis of the relation between dielectric constant and dielectric loss and temperature to obtain a curve of dielectric constant and dielectric loss with temperature as shown in FIG. 3, and according to FIG. 3, the ceramic sheet has a broad dispersion dielectric peak and shows obvious frequency dispersion phenomenon, indicating Sr 2+ Ion sum (Sn) 1/2 Hf 1/2 ) 4+ The ceramic doped with the composite ions has obvious relaxation characteristics; the ceramic plate is subjected to analysis of electric hysteresis loop and energy storage property, the obtained result is shown in figure 4, and according to figure 4, the electric hysteresis loop shows smaller hysteresis characteristic, the breakdown strength can reach 310kV/cm, and the releasable energy storage density can reach 4.04J/cm 3 The energy storage efficiency can reach 72%;
the ceramic wafer prepared in example 2 is analyzed by SEM, and the obtained microscopic morphology is characterized in that the characterization is shown in figure 5, and according to figure 5, the average size of the ceramic crystal grains is about 2.06 mu m, and the ceramic wafer is compact and has no obvious pores; the XRD pattern of the ceramic sheet was analyzed by an X-ray diffractometer, as shown in FIG. 6, and as can be seen from FIG. 6, sr 2+ Ion sum (Zr) 1/3 Sn 1/3 Hf 1/3 ) 4+ The composite ions enter perovskite lattices to form a single stable perovskite structure solid solution ceramic phase; the relation analysis of dielectric constant and dielectric loss and temperature is carried out on the ceramic sheet, the change curves of dielectric constant and dielectric loss with temperature are shown in figure 7, and according to figure 7, the ceramic sheet has a broad dispersion dielectric peak and obvious frequency dispersion phenomenon, which shows Sr 2+ Ion sum (Zr) 1/3 Sn 1/3 Hf 1/3 ) 4+ The ceramic doped with the composite ions has obvious relaxation characteristics; the ceramic plate is subjected to analysis of electric hysteresis loop and energy storage property, the obtained result is shown in figure 8, and according to figure 8, the electric hysteresis loop shows smaller hysteresis characteristic, the breakdown strength can reach 330kV/cm, and the releasable energy storage density can reach 4.4J/cm 3 The energy storage efficiency can reach 77%;
the ceramic sheet prepared in example 3 was analyzed by SEM to obtain a microstructure characterized in that as shown in FIG. 9, it can be seen from FIG. 9 that the ceramic grains were flatThe average size is about 2.05 mu m, and the porous ceramic material is compact and has no obvious pores; the XRD pattern of the ceramic sheet was analyzed by an X-ray diffractometer, as shown in FIG. 10, and as can be seen from FIG. 10, sr 2+ Ion sum (Al) 1/3 Hf 1/3 Ta 1/3 ) 4+ The composite ions enter perovskite lattices to form a single stable perovskite structure solid solution ceramic phase; the relation analysis of dielectric constant and dielectric loss and temperature is carried out on the ceramic sheet, the change curves of dielectric constant and dielectric loss with temperature are shown as figure 11, and according to figure 11, the ceramic sheet has a broad dispersion dielectric peak and obvious frequency dispersion phenomenon, which shows Sr 2+ Ion sum (Al) 1/3 Hf 1/3 Ta 1/3 ) 4+ The ceramic doped with the composite ions has obvious relaxation characteristics; the ceramic plate is subjected to analysis of electric hysteresis loop and energy storage property, the obtained result is shown in figure 12, and according to figure 12, the electric hysteresis loop shows smaller hysteresis characteristic, the breakdown strength can reach 280kV/cm, and the releasable energy storage density can reach 3.48J/cm 3 The energy storage efficiency can reach 78%;
the ceramic wafer prepared in example 4 was analyzed by SEM to obtain a microstructure with a representation shown in fig. 13, and according to fig. 13, it can be seen that the average size of the ceramic grains is about 3.29 μm, and the ceramic grains are dense and have no obvious pores; the XRD pattern of the ceramic sheet was analyzed by an X-ray diffractometer, as shown in FIG. 14, and as can be seen from FIG. 14, sr 2+ Ion sum (Mg) 1/5 Al 1/ 5 Ta 3/5 ) 4+ The composite ions enter perovskite lattices to form a single stable perovskite structure solid solution ceramic phase; the relation analysis of dielectric constant and dielectric loss and temperature is carried out on the ceramic sheet, the change curves of dielectric constant and dielectric loss with temperature are shown as figure 15, and according to figure 15, it can be seen that the ceramic sheet has a broad dispersion dielectric peak and shows obvious frequency dispersion phenomenon, which indicates Sr 2+ Ion sum (Mg) 1/5 Al 1/5 Ta 3/5 ) 4+ The ceramic doped with the composite ions has obvious relaxation characteristics; analyzing the hysteresis loop and the energy storage property of the ceramic plate to obtain a resultAs shown in FIG. 16, it can be seen from FIG. 16 that the hysteresis loop exhibits a small hysteresis characteristic, the breakdown strength of which can be up to 240kV/cm, and the releasable energy storage density of which can be up to 2.87J/cm 3 The energy storage efficiency can reach 85 percent.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. The composite ion modified sodium bismuth titanate-based energy storage ceramic material is characterized by having a general formula (Na) 0.5 Bi 0.5 ) 1-y Sr y Ti 1-x M x O 3 Wherein x is more than or equal to 0.05 and less than or equal to 0.20,0.20, y is more than or equal to 0.30;
wherein M is a complex ion (Sn 1/2 Hf 1/2 ) 4+ 、(Zr 1/3 Sn 1/3 Hf 1/3 ) 4+ 、(Al 1/3 Hf 1/3 Ta 1/3 ) 4+ 、(Mg 1/ 5 Al 1/5 Ta 3/5 ) 4+ One of them.
2. A method for preparing the composite ion modified sodium bismuth titanate based energy storage ceramic material as claimed in claim 1, comprising the steps of:
(1) And (3) batching: sodium carbonate, bismuth oxide, titanium oxide, strontium carbonate and M oxide are mixed according to the chemical formula (Na 0.5 Bi 0.5 ) 1-y Sr y Ti 1- x M x O 3 Mixing the mixture in a molar ratio of x being more than or equal to 0.05 and less than or equal to 0.20,0.20 and y being more than or equal to 0.30 to obtain a mixture;
(2) Mixing: adding absolute ethyl alcohol into the mixture, continuously ball milling, and uniformly mixing to form slurry;
(3) And (3) drying: drying the slurry at constant temperature to remove ethanol, and grinding to obtain uniformly mixed powder;
(4) Solid phase reaction: placing the powder in a mould, pressing and forming for 3-5 min under 150-200 MPa, placing the formed lump material in a solid-phase reaction furnace, preserving heat for 3-5 h at 850-1000 ℃ and carrying out solid-phase reaction;
(5) Ball milling: grinding the lump materials after the solid phase reaction to obtain ceramic powder, adding absolute ethyl alcohol into the ceramic powder, and continuously ball-milling to uniformly mix the powder to form ceramic slurry;
(6) And (3) drying: drying the ceramic slurry at constant temperature to remove ethanol, and grinding to obtain uniformly mixed ceramic powder;
(7) Granulating and forming: sieving ceramic powder, adding PVA solution, molding under 150-200 MPa, grinding, sieving to mix PVA with ceramic powder to obtain powder particles, placing the powder particles in a grinding tool, molding under 150-200 MPa, and isostatic pressing under 200-300 MPa to form ceramic green compact;
(8) And (3) glue discharging: preserving the heat of the ceramic green body, and discharging PVA in the ceramic green body to obtain a ceramic green body;
(9) Sintering: sintering the porcelain blank, and cooling to obtain the composite ion modified bismuth sodium titanate-based energy storage ceramic material.
3. The preparation method of the composite ion modified bismuth sodium titanate based energy storage ceramic material according to claim 2, wherein in the step (2), the addition amount of the absolute ethyl alcohol is 0.5-2 times of the mass of the mixture, and the ball milling time is 1-3 hours.
4. The preparation method of the composite ion modified bismuth sodium titanate based energy storage ceramic material according to claim 2, wherein in the step (5), the addition amount of the absolute ethyl alcohol is 0.5-2 times of the mass of the ceramic powder, and the ball milling time is 6-8 hours.
5. The method for preparing a composite ion modified bismuth sodium titanate based energy storage ceramic material according to claim 2, wherein in the step (7), the mass concentration of the PVA solution is 3%.
6. The method for preparing the composite ion modified bismuth sodium titanate based energy storage ceramic material according to claim 2, wherein in the step (8), the temperature of heat preservation is 500 ℃, and the time of heat preservation is 0.5-1 h.
7. The method for preparing the composite ion modified bismuth sodium titanate based energy storage ceramic material according to claim 2, wherein in the step (9), the sintering temperature is 1000-1200 ℃, and the sintering time is 2-3 h.
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