CN114914088A - High-energy-storage silver niobate ceramic capacitor and preparation method thereof - Google Patents
High-energy-storage silver niobate ceramic capacitor and preparation method thereof Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 72
- 239000004332 silver Substances 0.000 title claims abstract description 72
- 238000004146 energy storage Methods 0.000 title claims abstract description 65
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000919 ceramic Substances 0.000 claims abstract description 51
- 238000000498 ball milling Methods 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 42
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 21
- 235000015895 biscuits Nutrition 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 238000003826 uniaxial pressing Methods 0.000 claims abstract description 15
- 238000005469 granulation Methods 0.000 claims abstract description 11
- 230000003179 granulation Effects 0.000 claims abstract description 11
- 239000003292 glue Substances 0.000 claims abstract description 10
- 238000005498 polishing Methods 0.000 claims abstract description 10
- 238000007639 printing Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 230000005684 electric field Effects 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 230000010287 polarization Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 238000003825 pressing Methods 0.000 description 13
- 238000000465 moulding Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011363 dried mixture Substances 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 3
- 230000005620 antiferroelectricity Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a high energy storage silver niobate ceramic capacitor and a preparation method thereof, wherein the silver niobate ceramic material in the silver niobate ceramic capacitor is of a single perovskite structure; the energy storage density of the silver niobate ceramic material is 2.4J/cm at room temperature 3 ～4.8J/cm 3 (ii) a The preparation method comprises the following steps: mixing Ag 2 O powder and Nb 2 O 5 Sequentially carrying out ball milling, mixing, drying and tabletting on the powder to obtain a green body; pre-sintering the green body in oxygen to obtain a rough blank; grinding and crushing the rough blank, and then sequentially carrying out ball milling, drying, granulation and high-pressure uniaxial pressing forming to prepare a biscuit; removing the glue from the biscuit, and sintering in oxygen to obtain a ceramic wafer; and grinding and polishing the ceramic wafer into a ceramic sheet, printing silver electrodes on two surfaces of the ceramic sheet, calcining and cooling. The invention can improve the energy storage performance of the silver niobate ceramic.
Description
Technical Field
The invention belongs to the technical field of functional ceramic materials, and relates to a high-energy-storage silver niobate ceramic capacitor and a preparation method thereof.
Background
As the conflict between fossil fuel shortages and increased energy demand increases, efficient storage and utilization of energy becomes increasingly important. Due to the ultrahigh power density and the charge-discharge speed, the dielectric capacitor is widely applied to various scenes and is considered to be a promising energy storage device in a pulse power system. The dielectric material is the core component of the dielectric capacitor and directly determines the performance of the dielectric capacitor. Of all dielectric materials, antiferroelectric energy storage ceramics with lower remanent polarization and higher energy storage efficiency have received much attention from researchers.
Silver niobate-based ceramics have gradually become a new green lead-free energy storage material which attracts attention in recent years due to lower sintering temperature and excellent antiferroelectricity. 2018 Wang et al prepared pure AgNbO by adopting conventional solid-phase reaction method 3 The ceramic has low energy storage density and energy storage efficiency. Currently, research on silver niobate-based lead-free energy storage ceramics mainly focuses on improving the energy storage performance of a system through doping modification, however, other ions need to be introduced through doping modification, different preparation processes need to be repeatedly searched, and the process is complicated and the cost is high.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a high-energy-storage silver niobate ceramic capacitor and a preparation method thereof, which can improve the energy storage performance of silver niobate ceramic.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
on one hand, the invention provides a high energy storage silver niobate ceramic capacitor, wherein the silver niobate ceramic material in the silver niobate ceramic capacitor is of a single perovskite structure; the energy storage density of the silver niobate ceramic material is 2.4J/cm at room temperature 3 ～4.8J/cm 3 。
Optionally, the breakdown electric field of the silver niobate ceramic material is 175 kV/cm-342 kV/cm at room temperature.
Optionally, the polarization strength of the silver niobate ceramic material at room temperature is 33 μ C/cm 2 ~52μC/cm 2 。
Optionally, the energy storage efficiency of the silver niobate ceramic material is 42-46% at room temperature.
On the other hand, the invention provides a preparation method of the high-energy-storage silver niobate ceramic capacitor, which comprises the following steps:
mixing Ag with water 2 O powder and Nb 2 O 5 Sequentially carrying out ball milling, mixing, drying and tabletting on the powder to obtain a green body;
pre-sintering the green body in oxygen to obtain a rough blank;
grinding and crushing the rough blank, and then sequentially carrying out ball milling, drying, granulation and high-pressure uniaxial pressing forming to prepare a biscuit;
removing the adhesive from the biscuit, and sintering in oxygen to obtain a ceramic wafer;
and grinding and polishing the ceramic wafer into a ceramic sheet, printing silver electrodes on two surfaces of the ceramic sheet, calcining and cooling.
Optionally, in the process of preparing the biscuit, the uniaxial pressing pressure adopted in the uniaxial pressing molding is 120xMPa, wherein 2 is less than or equal tox≤7。
Optionally, Ag 2 O powder and Nb 2 O 5 The powder is mixed according to the mass ratio of 1:1, and the uniaxial tabletting pressure adopted in tabletting is 150-300 MPa in the process of preparing a green body.
Optionally, during granulation, the selected adhesive is a polyvinyl alcohol solution with the mass fraction of 5%, and the adding amount of the adhesive is 4-6% of the mass of the powder.
Optionally, pre-burning for 4-6 h at 850-950 ℃; discharging glue for 2h at the temperature of 600 ℃; sintering for 4-6 h at 1060-1080 ℃.
Optionally, the thickness of the ceramic sheet is 0.10 mm-0.20 mm; calcining at 580-600 ℃ for 20-30 min.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a high-energy-storage silver niobate ceramic capacitor and a preparation method thereof, which abandons the mode of doping modification, does not introduce other elements, does not need to search for the preparation process thereof, and only regulates and controls the uniaxial pressing pressure adopted during the preparation of biscuitOptimized AgNbO 3 The energy storage ceramic has the structure, so the preparation cost is low, and the preparation process is simple and easy to operate;
pure AgNbO prepared by the invention 3 The energy storage ceramic has the advantages of high energy storage density, high breakdown electric field, high polarization strength and the like, and has excellent energy storage performance.
Drawings
FIG. 1 is an XRD pattern of a ceramic sample prepared according to an embodiment of the present invention;
FIG. 2 is a hysteresis loop of a ceramic sample prepared according to an example of the present invention;
FIG. 3 is a graph of the hysteresis loop and the electric field-current relationship of a ceramic sample prepared according to an embodiment of the present invention;
FIG. 4 is a graph of phase change electric field versus pressure for ceramic samples prepared in accordance with an embodiment of the present invention;
FIG. 5 is a graph of energy storage density and energy storage efficiency versus pressure for ceramic samples prepared in accordance with an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate a number of the indicated technical features. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The first embodiment is as follows:
as shown in fig. 1, fig. 2, fig. 4 and fig. 5, a method for preparing a high energy storage silver niobate ceramic capacitor includes the following steps:
s1, mixing high-purity Ag 2 O powder and Nb 2 O 5 Weighing powder according to the mass ratio of 1:1, pouring the weighed powder into an agate ball-milling tank, adding absolute ethyl alcohol as a ball-milling solvent, mixing and ball-milling for 24 hours at the ball-milling rotating speed of 300 revolutions per minute, and drying the ball-milled mixture in an oven at 80 ℃ for 12 hours after ball milling; manually grinding the dried mixture for 40 minutes, and pressing the mixture into a green body with the diameter of 20mm by adopting 150Mpa pressure;
s2, placing the green body in oxygen, pre-sintering for 6 hours at 880 ℃, wherein the heating and cooling rates are both 5 ℃/min, and obtaining a rough blank;
s3, grinding the rough blank, then performing ball milling and drying in sequence, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulation, wherein the adding mass of the polyvinyl alcohol solution is 5% of the mass of the powder; performing uniaxial pressing molding on the granulated powder by adopting the pressure of 240MPa, and pressing into a biscuit with the diameter of 8mm and the thickness of 1.5 mm;
s4, placing the biscuit in oxygen, discharging glue for 2 hours at 600 ℃, then heating to 1065 ℃, and then preserving heat for 6 hours, wherein the heating and cooling rates are both 5 ℃/min, so as to prepare a ceramic wafer;
s5, polishing the ceramic wafer,Polishing to 0.15mm thin slices, sequentially performing ultrasonic cleaning and drying, respectively printing silver electrodes with the diameter of 2mm on two surfaces of a ceramic wafer in a screen printing mode, baking for 20min in a tube furnace at the temperature of 600 ℃, and naturally cooling to obtain AgNbO to be measured 3 (x=2) ceramic capacitor samples.
AgNbO to be tested 3 (x=2) the silver niobate ceramic material in the ceramic capacitor is of a single perovskite structure; the breakdown electric field of the silver niobate ceramic material is 175kV/cm at room temperature; the energy storage density of the silver niobate ceramic material is 2.4J/cm at room temperature 3 The energy storage efficiency is 42%.
Example two:
as shown in fig. 1, fig. 2, fig. 4 and fig. 5, a method for preparing a high energy storage silver niobate ceramic capacitor includes the following steps:
s1, mixing high-purity Ag 2 O powder and Nb 2 O 5 Weighing the powder according to the ratio of 1:1 of the weight of the materials, pouring the weighed powder into an agate ball milling tank, adding absolute ethyl alcohol as a ball milling solvent, mixing and ball milling for 24 hours, wherein the ball milling rotation speed is 300 r/min, and after ball milling is finished, drying the ball-milled mixture in an oven at 80 ℃ for 12 hours; manually grinding the dried mixture for 40 minutes, and pressing the mixture into a green body with the diameter of 20mm by adopting the pressure of 200 Mpa;
s2, pre-sintering the green body in oxygen at 900 ℃ for 5 hours, wherein the heating and cooling rates are both 5 ℃/min, and obtaining a rough blank;
s3, grinding the rough blank, then performing ball milling and drying in sequence, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulation, wherein the adding mass of the polyvinyl alcohol solution is 5% of the mass of the powder; performing uniaxial pressing molding on the granulated powder by adopting the pressure of 360MPa, and pressing into a biscuit with the diameter of 8mm and the thickness of 1.5 mm;
s4, placing the biscuit in oxygen, discharging glue for 2 hours at 600 ℃, then heating to 1070 ℃, and then preserving heat for 6 hours, wherein the heating and cooling rates are both 5 ℃/min, so as to prepare a ceramic wafer;
s5, grinding and polishing the ceramic wafer to 0.15mm thin slices, and sequentially feedingUltrasonic cleaning and drying, respectively printing silver electrodes with the diameter of 2mm on two sides of a ceramic wafer by a screen printing mode, baking for 25min in a tube furnace at the temperature of 600 ℃, and naturally cooling to obtain AgNbO to be measured 3 (x=3) ceramic capacitor samples.
AgNbO to be detected 3 (x=3) the silver niobate ceramic material in the ceramic capacitor is of a single perovskite structure; the breakdown electric field of the silver niobate ceramic material is 217kV/cm at room temperature; the energy storage density of the silver niobate ceramic material is 3.3J/cm at room temperature 3 The energy storage efficiency was 43.5%.
Example three:
as shown in fig. 1, fig. 2, fig. 4 and fig. 5, a method for preparing a high energy storage silver niobate ceramic capacitor includes the following steps:
s1, mixing high-purity Ag 2 O powder and Nb 2 O 5 Weighing the powder according to the ratio of 1:1 of the weight of the materials, pouring the weighed powder into an agate ball milling tank, adding absolute ethyl alcohol as a ball milling solvent, mixing and ball milling for 24 hours, wherein the ball milling rotation speed is 300 r/min, and after ball milling is finished, drying the ball-milled mixture in an oven at 80 ℃ for 12 hours; manually grinding the dried mixture for 40 minutes, and pressing the mixture into a green body with the diameter of 20mm by adopting 150Mpa pressure;
s2, pre-sintering the green body in oxygen at 900 ℃ for 6 hours, wherein the heating and cooling rates are both 5 ℃/min, and obtaining a rough blank;
s3, grinding the rough blank, then performing ball milling and drying in sequence, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulation, wherein the adding mass of the polyvinyl alcohol solution is 5% of the mass of the powder; performing uniaxial pressing molding on the granulated powder by adopting 480MPa pressure, and pressing into a biscuit with the diameter of 8mm and the thickness of 1.5 mm;
s4, placing the biscuit in oxygen, discharging glue for 2 hours at 600 ℃, then heating to 1065 ℃, and then preserving heat for 6 hours, wherein the heating and cooling rates are both 5 ℃/min, so as to prepare a ceramic wafer;
s5, grinding and polishing the ceramic wafer to 0.14mm thin sheet, and sequentially carrying out ultrasonic cleaning and drying, and then introducingPrinting silver electrodes with the diameter of 2mm on two surfaces of the ceramic wafer respectively in a screen printing mode, baking for 30min in a tube furnace at the temperature of 600 ℃, and naturally cooling to obtain AgNbO to be measured 3 (x=4) ceramic capacitor samples.
AgNbO to be detected 3 (x=4) the silver niobate ceramic material in the ceramic capacitor is of a single perovskite structure; the breakdown electric field of the silver niobate ceramic material is 265kV/cm at room temperature; the energy storage density of the silver niobate ceramic material is 4.2J/cm at room temperature 3 The energy storage efficiency is 44%.
Example four:
as shown in fig. 1 to 5, a method for preparing a high energy storage silver niobate ceramic capacitor includes the following steps:
s1, mixing high-purity Ag 2 O powder and Nb 2 O 5 Weighing the powder according to the ratio of 1:1 of the weight of the materials, pouring the weighed powder into an agate ball milling tank, adding absolute ethyl alcohol as a ball milling solvent, mixing and ball milling for 24 hours, wherein the ball milling rotation speed is 300 r/min, and after ball milling is finished, drying the ball-milled mixture in an oven at 80 ℃ for 12 hours; manually grinding the dried mixture for 40 minutes, and pressing the mixture into a green body with the diameter of 20mm by adopting the pressure of 250 Mpa;
s2, placing the green body in oxygen, pre-sintering for 5 hours at 880 ℃, wherein the heating and cooling rates are both 5 ℃/min, and obtaining a rough blank;
s3, grinding the rough blank, then performing ball milling and drying in sequence, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulation, wherein the adding mass of the polyvinyl alcohol solution is 5% of the mass of the powder; performing uniaxial pressing molding on the granulated powder by adopting the pressure of 600MPa, and pressing into a biscuit with the diameter of 8mm and the thickness of 1.5 mm;
s4, placing the biscuit in oxygen, discharging glue for 2 hours at 600 ℃, then heating to 1065 ℃, and then preserving heat for 6 hours, wherein the heating and cooling rates are both 5 ℃/min, so as to prepare a ceramic wafer;
s5, polishing the ceramic wafer to 0.12mm thin sheet, ultrasonic cleaning and drying in turn, and then respectively arranging two sides of the ceramic wafer by silk screen printingPrinting a silver electrode with the diameter of 2mm, baking for 20min in a tube furnace at the temperature of 600 ℃, and naturally cooling to obtain AgNbO to be measured 3 (x=5) ceramic capacitor samples.
AgNbO to be tested 3 (x=5) the silver niobate ceramic material in the ceramic capacitor is of a single perovskite structure; the breakdown electric field of the silver niobate ceramic material is 310kV/cm at room temperature; the energy storage density of the silver niobate ceramic material is 4.8J/cm at room temperature 3 The energy storage efficiency was 45%.
Example five:
as shown in fig. 1, fig. 2, fig. 4 and fig. 5, a method for preparing a high energy storage silver niobate ceramic capacitor includes the following steps:
s1, mixing high-purity Ag 2 O powder and Nb 2 O 5 Weighing the powder according to the ratio of 1:1 of the weight of the materials, pouring the weighed powder into an agate ball milling tank, adding absolute ethyl alcohol as a ball milling solvent, mixing and ball milling for 24 hours, wherein the ball milling rotation speed is 300 r/min, and after ball milling is finished, drying the ball-milled mixture in an oven at 80 ℃ for 12 hours; manually grinding the dried mixture for 40 minutes, and pressing the mixture into a green body with the diameter of 20mm by adopting the pressure of 200 Mpa;
s2, pre-sintering the green body in oxygen at 900 ℃ for 6 hours, wherein the heating and cooling rates are both 5 ℃/min, and obtaining a rough blank;
s3, grinding the rough blank, then performing ball milling and drying in sequence, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulation, wherein the adding mass of the polyvinyl alcohol solution is 5% of the mass of the powder; performing uniaxial pressing molding on the granulated powder by adopting 720MPa pressure, and pressing into a biscuit with the diameter of 8mm and the thickness of 1.5 mm;
s4, placing the biscuit in oxygen, discharging glue for 2 hours at 600 ℃, then heating to 1070 ℃, and then preserving heat for 6 hours, wherein the heating and cooling rates are both 5 ℃/min, so as to prepare a ceramic wafer;
s5, grinding and polishing the ceramic wafer to 0.15mm thin sheet, sequentially carrying out ultrasonic cleaning and drying, then respectively printing silver electrodes with the diameter of 2mm on the two sides of the ceramic wafer in a screen printing mode, and finally, printing silver electrodes on the two sides of the ceramic wafer in a screen printing modeBaking the mixture for 20min at 600 ℃ in a tube furnace, and naturally cooling the mixture to obtain AgNbO to be detected 3 (x=6) ceramic capacitor samples.
AgNbO to be tested 3 (x=6) the silver niobate ceramic material in the ceramic capacitor is of a single perovskite structure; the breakdown electric field of the silver niobate ceramic material is 322kV/cm at room temperature; the energy storage density of the silver niobate ceramic material is 3.9J/cm at room temperature 3 The energy storage efficiency was 45%.
Example six:
as shown in fig. 1, fig. 2, fig. 4 and fig. 5, a method for preparing a high energy storage silver niobate ceramic capacitor includes the following steps:
s1, mixing high-purity Ag 2 O powder and Nb 2 O 5 Weighing the powder according to the ratio of 1:1 of the weight of the materials, pouring the weighed powder into an agate ball milling tank, adding absolute ethyl alcohol as a ball milling solvent, mixing and ball milling for 24 hours, wherein the ball milling rotation speed is 300 r/min, and after ball milling is finished, drying the ball-milled mixture in an oven at 80 ℃ for 12 hours; manually grinding the dried mixture for 40 minutes, and pressing the mixture into a green body with the diameter of 20mm by adopting the pressure of 200 Mpa;
s2, pre-sintering the green body in oxygen at 900 ℃ for 6 hours, wherein the heating and cooling rates are both 5 ℃/min, and obtaining a rough blank;
s3, grinding the rough blank, then performing ball milling and drying in sequence, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulation, wherein the adding mass of the polyvinyl alcohol solution is 5% of the mass of the powder; performing uniaxial pressing molding on the granulated powder by adopting the pressure of 840MPa, and pressing into a biscuit with the diameter of 8mm and the thickness of 1.5 mm;
s4, placing the biscuit in oxygen, discharging glue for 2 hours at 600 ℃, then heating to 1065 ℃, and then preserving heat for 6 hours, wherein the heating and cooling rates are both 5 ℃/min, so as to prepare a ceramic wafer;
s5, polishing the ceramic wafer to 0.13mm thin slice, ultrasonic cleaning and drying in sequence, then respectively printing silver electrodes with the diameter of 2mm on the two sides of the ceramic wafer by a screen printing mode, baking for 25min in a tube furnace at 600 ℃, and then automatically dryingThen cooling to obtain AgNbO to be measured 3 (x=7) ceramic capacitor sample.
AgNbO to be tested 3 (x=7) the silver niobate ceramic material in the ceramic capacitor is of a single perovskite structure; the breakdown electric field of the silver niobate ceramic material is 342kV/cm at room temperature; the energy storage density of the silver niobate ceramic material is 3.4J/cm at room temperature 3 The energy storage efficiency was 46%.
The following table shows the performance parameters of the energy storage ceramics prepared in examples 1 to 6 of the present invention:
| uniaxial pressure | Maximum electric field E m | Energy storage density W rec | Efficiency eta | |
| Example 1 | 240Mpa | 175 kV/cm | 2.4 J/cm 3 | 42% |
| Example 2 | 360Mpa | 217 kV/cm | 3.3 J/cm 3 | 43.5% |
| Example 3 | 480Mpa | 265 kV/cm | 4.2 J/cm 3 | 44% |
| Example 4 | 600Mpa | 310 kV/cm | 4.8 J/cm 3 | 45% |
| Example 5 | 720Mpa | 322 kV/cm | 3.9 J/cm 3 | 45% |
| Example 6 | 840Mpa | 342 kV/cm | 3.4J/ |
46% |
The ceramic samples prepared in examples 1-6 were all single perovskite structures, and no impurity phase appeared in the XRD accuracy range. As shown in fig. 1, the (020) peak, the (220) peak and the (008) peak are shifted to high angles, which indicates that the lattice parameter is reduced, the unit cell volume is reduced, i.e., the lattice is shrunk, and the antiferroelectricity of the system is enhanced with the increase of the pressure. As can be seen from fig. 2, as the sheet pressing pressure increases, the hysteresis loop becomes narrower, and the maximum breakdown field strength and the phase-change electric field increase. As can be seen from fig. 4, the difference (EF-EA) between the positive and negative phase-change electric fields gradually decreases with increasing pressure, and therefore the energy storage efficiency increases. As can be seen from FIG. 5, the ceramic sample prepared in example 4 has the highest energy storage density, which is as high as 4.8J/cm3, and the energy storage efficiency can reach 45%.
Under the condition of not introducing other elements, the invention adopts a new idea of mechanical constraint, optimizes the structure of the silver niobate energy storage ceramic by regulating and controlling the uniaxial pressing pressure, enhances the antiferroelectric property and can obtain the lead-free energy storage ceramic with high energy storage density, high breakdown electric field and high polarization strength.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The high-energy-storage silver niobate ceramic capacitor is characterized in that: the silver niobate ceramic material in the silver niobate ceramic capacitor is of a single perovskite structure; the energy storage density of the silver niobate ceramic material is 2.4J/cm at room temperature 3 ～4.8J/cm 3 。
2. The high energy storage silver niobate ceramic capacitor of claim 1, wherein: the breakdown electric field of the silver niobate ceramic material is 175 kV/cm-342 kV/cm at room temperature.
3. The high energy storage silver niobate ceramic capacitor of claim 1, wherein: the polarization strength of the silver niobate ceramic material is 33 mu C/cm at room temperature 2 ~52μC/cm 2 。
4. The high energy storage silver niobate ceramic capacitor of claim 1, wherein: the energy storage efficiency of the silver niobate ceramic material is 42-46% at room temperature.
5. The method for preparing the high energy storage silver niobate ceramic capacitor according to any one of claims 1 to 4, comprising the following steps:
mixing Ag with water 2 O powder and Nb 2 O 5 Sequentially carrying out ball milling, mixing, drying and tabletting on the powder to obtain a green body;
pre-sintering the green body in oxygen to obtain a rough blank;
grinding and crushing the rough blank, and then sequentially carrying out ball milling, drying, granulation and high-pressure uniaxial pressing forming to prepare a biscuit;
removing the glue from the biscuit, and sintering in oxygen to obtain a ceramic wafer;
and grinding and polishing the ceramic wafer into a ceramic sheet, printing silver electrodes on two surfaces of the ceramic sheet, calcining and cooling.
6. The method for preparing the high-energy-storage silver niobate ceramic capacitor according to claim 5, characterized in that: in the process of producing a biscuit, the uniaxial pressing pressure used in the uniaxial pressing is 120xMPa, wherein 2 is less than or equal tox≤7。
7. The method for preparing the high-energy-storage silver niobate ceramic capacitor according to claim 5, characterized in that: ag 2 O powder and Nb 2 O 5 The powder is mixed according to the mass ratio of 1:1, and the uniaxial tabletting pressure adopted in tabletting is 150-300 MPa in the process of preparing a green body.
8. The method for preparing the high-energy-storage silver niobate ceramic capacitor according to claim 5, characterized in that: during granulation, the selected adhesive is a polyvinyl alcohol solution with the mass fraction of 5%, and the adding amount of the adhesive is 4-6% of the mass of the powder.
9. The method for preparing the high-energy-storage silver niobate ceramic capacitor according to claim 5, characterized in that: pre-burning for 4-6 h at 850-950 ℃; discharging glue for 2h at the temperature of 600 ℃; sintering for 4-6 h at 1060-1080 ℃.
10. The method for preparing the high-energy-storage silver niobate ceramic capacitor according to claim 5, characterized in that: the thickness of the ceramic sheet is 0.10 mm-0.20 mm; calcining at 580-600 ℃ for 20-30 min.
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