CN114914088B - 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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- CN114914088B CN114914088B CN202210573974.3A CN202210573974A CN114914088B CN 114914088 B CN114914088 B CN 114914088B CN 202210573974 A CN202210573974 A CN 202210573974A CN 114914088 B CN114914088 B CN 114914088B
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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 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 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
- 238000000227 grinding Methods 0.000 claims abstract description 24
- 238000001816 cooling 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
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000005498 polishing Methods 0.000 claims abstract description 9
- 238000007639 printing Methods 0.000 claims abstract description 9
- 238000003826 uniaxial pressing Methods 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 230000005684 electric field Effects 0.000 claims description 13
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 8
- 230000010287 polarization Effects 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- 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
- 239000003292 glue Substances 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000005620 antiferroelectricity Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 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
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Classifications
-
- 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 silver niobate ceramic capacitor with high energy storage and a preparation method thereof, wherein silver niobate ceramic material in the silver niobate ceramic capacitor has a single perovskite structure; at room temperature, the energy storage density of the silver niobate ceramic material is 2.4J/cm 3 ～4.8J/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The preparation method comprises the following steps: ag with 2 O powder and Nb 2 O 5 Sequentially performing ball milling mixing, drying and tabletting on the powder to prepare a green body; placing the green body in oxygen for presintering to obtain a rough blank; grinding and crushing the rough blank, and then sequentially performing ball milling, drying, granulating and high-pressure uniaxial pressing and forming to obtain 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 sides of the ceramic sheet, calcining and cooling. The invention can improve the energy storage performance of silver niobate ceramics.
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 demands increases, efficient storage and utilization of energy becomes increasingly important. Dielectric capacitors are widely used in a variety of contexts, thanks to their ultra-high power density and charge-discharge speed, and are considered as promising energy storage devices in pulsed power systems. The dielectric material is the core component of the dielectric capacitor and directly determines the performance of the dielectric capacitor. Antiferroelectric energy storage ceramics with lower remnant polarization and higher energy storage efficiency have received extensive attention from researchers among all dielectric materials.
Silver niobate-based ceramics have been recently attracting attention as a novel green lead-free energy storage material with a low sintering temperature and excellent antiferroelectricity.2018 Wang et al prepared pure AgNbO by conventional solid phase reaction method 3 Ceramics have low energy storage density and low energy storage efficiency. The current research of silver niobate-based leadless energy storage ceramics mainly focuses on improving the energy storage performance of a system through doping modification, however, other ions need to be introduced during doping modification, and different preparation processes need to be repeatedly searched, so that 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 above purpose, the invention is realized by adopting the following technical scheme:
in one aspect, the invention provides a silver niobate ceramic capacitor with high energy storage, wherein silver niobate ceramic material in the silver niobate ceramic capacitor has a single perovskite structure; at room temperature, the energy storage density of the silver niobate ceramic material is 2.4J/cm 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.
Alternatively, the silver niobate ceramic material has a polarization strength of 33 μC/cm at room temperature 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:
ag with 2 O powder and Nb 2 O 5 Sequentially performing ball milling mixing, drying and tabletting on the powder to prepare a green body;
placing the green body in oxygen for presintering to obtain a rough blank;
grinding and crushing the rough blank, and then sequentially performing ball milling, drying, granulating and high-pressure uniaxial pressing and forming to obtain 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 sides of the ceramic sheet, calcining and cooling.
Optionally, in the process of preparing the biscuit, the uniaxial pressing pressure adopted in uniaxial pressing is 120xMPa, wherein 2 is less than or equal tox≤7。
Alternatively, ag 2 O powder and Nb 2 O 5 Mixing the powder according to the mass ratio of 1:1, wherein the uniaxial tabletting pressure adopted in the tabletting process is 150 mpa-300 mpa in the process of preparing green bodies.
Optionally, during granulation, the selected adhesive is a polyvinyl alcohol solution with the mass fraction of 5%, and the addition amount of the adhesive is 4% -6% of the mass of the powder.
Optionally, presintering for 4-6 hours at 850-950 ℃; discharging the adhesive for 2 hours at 600 ℃; sintering for 4-6 h at 1060-1080 ℃.
Optionally, the thickness of the ceramic sheet is 0.10 mm-0.20 mm; calcining for 20-30 min at 580-600 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a silver niobate ceramic capacitor with high energy storage and a preparation method thereof, which abandons a doping modification mode, does not introduce other elements, does not need to fuze a preparation process, and optimizes AgNbO by regulating and controlling uniaxial pressing pressure adopted in preparing a biscuit 3 The energy storage ceramic has a structure, so that 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 intensity and the like, and has excellent energy storage performance.
Drawings
FIG. 1 is an XRD pattern of a ceramic sample prepared in accordance with an embodiment of the present invention;
FIG. 2 is a graph showing the hysteresis loop of a ceramic sample prepared according to an embodiment of the present invention;
FIG. 3 is a graph showing the relationship between the hysteresis loop and the electric field-current of a ceramic sample prepared according to an embodiment of the present invention;
FIG. 4 is a graph of the phase change electric field versus pressure for a ceramic sample 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 more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not 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 a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first", "a second", etc. may explicitly or implicitly include one or more such feature. In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication 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 in a specific case.
Embodiment one:
as shown in fig. 1, 2, 4 and 5, a preparation method of a silver niobate ceramic capacitor with high energy storage comprises the following steps:
s1, high-purity Ag 2 O powder and Nb 2 O 5 Weighing the 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, wherein the ball milling rotating speed is 300 revolutions per minute, and after ball milling, placing the ball-milled mixture into an oven at 80 ℃ for drying for 12 hours; manually grinding the dried mixture for 40 minutes, and then pressing the mixture into a green body with the diameter of 20mm by adopting 150Mpa pressure;
s2, placing the green body in oxygen, presintering for 6 hours at the temperature of 880 ℃, wherein the heating and cooling rates are 5 ℃/min, and preparing a rough blank;
s3, grinding the rough blank, sequentially performing ball milling and drying, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulating, wherein the added mass of the polyvinyl alcohol solution is 5% of the mass of the powder; carrying out uniaxial compression 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 preserving heat for 6 hours, wherein the heating and cooling rates are 5 ℃/min, and preparing the ceramic wafer;
s5, grinding and polishing the ceramic wafer to a sheet with the thickness of 0.15mm, sequentially carrying out ultrasonic cleaning and drying, printing silver electrodes with the diameter of 2mm on two sides of the ceramic wafer in a screen printing mode, baking for 20min in a tubular furnace at 600 ℃, and naturally cooling to obtain AgNbO to be tested 3 (x=2) ceramic capacitor samples.
AgNbO to be measured 3 (x=2) silver niobate ceramic material in ceramic capacitor is of single perovskite structure; at room temperature, 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 3 The energy storage efficiency was 42%.
Embodiment two:
as shown in fig. 1, 2, 4 and 5, a preparation method of a silver niobate ceramic capacitor with high energy storage comprises the following steps:
s1, high-purity Ag 2 O powder and Nb 2 O 5 Weighing the 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, wherein the ball milling rotating speed is 300 revolutions per minute, and after ball milling, placing the ball-milled mixture into an oven at 80 ℃ for drying for 12 hours; manually grinding the dried mixture for 40 minutes, and then pressing the mixture into a green body with the diameter of 20mm by adopting 200Mpa pressure;
s2, placing the green body in oxygen, presintering for 5 hours at 900 ℃, wherein the heating and cooling rates are 5 ℃/min, and preparing a rough blank;
s3, grinding the rough blank, sequentially performing ball milling and drying, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulating, wherein the added mass of the polyvinyl alcohol solution is 5% of the mass of the powder; carrying out uniaxial compression 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 preserving heat for 6 hours, wherein the temperature and the cooling rate are 5 ℃/min, and the ceramic wafer is prepared;
s5, grinding and polishing the ceramic wafer to a sheet with the thickness of 0.15mm, sequentially carrying out ultrasonic cleaning and drying, printing silver electrodes with the diameter of 2mm on two sides of the ceramic wafer in a screen printing mode, baking for 25min in a tubular furnace at 600 ℃, and naturally cooling to obtain AgNbO to be tested 3 (x=3) ceramic capacitor samples.
AgNbO to be measured 3 (x=3) silver niobate ceramic material in ceramic capacitor is of single perovskite structure; at room temperature, 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 3 The energy storage efficiency is 43.5%.
Embodiment III:
as shown in fig. 1, 2, 4 and 5, a preparation method of a silver niobate ceramic capacitor with high energy storage comprises the following steps:
s1, high-purity Ag 2 O powder and Nb 2 O 5 Weighing the 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, wherein the ball milling rotating speed is 300 revolutions per minute, and after ball milling, placing the ball-milled mixture into an oven at 80 ℃ for drying for 12 hours; manually grinding the dried mixture for 40 minutes, and then pressing the mixture into a green body with the diameter of 20mm by adopting 150Mpa pressure;
s2, placing the green body in oxygen, presintering for 6 hours at 900 ℃, wherein the heating and cooling rates are 5 ℃/min, and preparing a rough blank;
s3, grinding the rough blank, sequentially performing ball milling and drying, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulating, wherein the added mass of the polyvinyl alcohol solution is 5% of the mass of the powder; monoaxially pressing the granulated powder by adopting the pressure of 480MPa to form 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 preserving heat for 6 hours, wherein the heating and cooling rates are 5 ℃/min, and preparing the ceramic wafer;
s5, grinding and polishing the ceramic wafer to a sheet with the thickness of 0.14mm, sequentially carrying out ultrasonic cleaning and drying, printing silver electrodes with the diameter of 2mm on two sides of the ceramic wafer in a screen printing mode, baking for 30min in a tubular furnace at 600 ℃, and naturally cooling to obtain AgNbO to be tested 3 (x=4) ceramic capacitor samples.
AgNbO to be measured 3 (x=4) silver niobate ceramic material in ceramic capacitor is of single perovskite structure; at room temperature, 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 3 The energy storage efficiency was 44%.
Embodiment four:
as shown in fig. 1 to 5, a method for preparing a silver niobate ceramic capacitor with high energy storage comprises the following steps:
s1, high-purity Ag 2 O powder and Nb 2 O 5 Weighing the 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, wherein the ball milling rotating speed is 300 revolutions per minute, and after ball milling, placing the ball-milled mixture into an oven at 80 ℃ for drying for 12 hours; manually grinding the dried mixture for 40 minutes, and then pressing the mixture into a green body with the diameter of 20mm by adopting 250Mpa pressure;
s2, placing the green body in oxygen, presintering for 5 hours at the temperature of 880 ℃, wherein the heating and cooling rates are 5 ℃/min, and preparing a rough blank;
s3, grinding the rough blank, sequentially performing ball milling and drying, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulating, wherein the added mass of the polyvinyl alcohol solution is 5% of the mass of the powder; carrying out uniaxial compression 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 preserving heat for 6 hours, wherein the heating and cooling rates are 5 ℃/min, and preparing the ceramic wafer;
s5, grinding and polishing the ceramic wafer to a sheet with the thickness of 0.12mm, sequentially carrying out ultrasonic cleaning and drying, printing silver electrodes with the diameter of 2mm on two sides of the ceramic wafer in a screen printing mode, baking for 20min in a tubular furnace at 600 ℃, and naturally cooling to obtain AgNbO to be tested 3 (x=5) ceramic capacitor samples.
AgNbO to be measured 3 (x=5) silver niobate ceramic material in ceramic capacitor is of single perovskite structure; at room temperature, 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 3 The energy storage efficiency is 45%.
Fifth embodiment:
as shown in fig. 1, 2, 4 and 5, a preparation method of a silver niobate ceramic capacitor with high energy storage comprises the following steps:
s1, high-purity Ag 2 O powder and Nb 2 O 5 Weighing the 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, wherein the ball milling rotating speed is 300 revolutions per minute, and after ball milling, placing the ball-milled mixture into an oven at 80 ℃ for drying for 12 hours; manually grinding the dried mixture for 40 minutes, and then pressing the mixture into a green body with the diameter of 20mm by adopting 200Mpa pressure;
s2, placing the green body in oxygen, presintering for 6 hours at 900 ℃, wherein the heating and cooling rates are 5 ℃/min, and preparing a rough blank;
s3, grinding the rough blank, sequentially performing ball milling and drying, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulating, wherein the added mass of the polyvinyl alcohol solution is 5% of the mass of the powder; carrying out uniaxial compression molding on the granulated powder by adopting the pressure of 720MPa, 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 preserving heat for 6 hours, wherein the temperature and the cooling rate are 5 ℃/min, and the ceramic wafer is prepared;
s5, grinding and polishing the ceramic wafer to a sheet with the thickness of 0.15mm, sequentially carrying out ultrasonic cleaning and drying, printing silver electrodes with the diameter of 2mm on two sides of the ceramic wafer in a screen printing mode, baking for 20min in a tubular furnace at 600 ℃, and naturally cooling to obtain AgNbO to be tested 3 (x=6) ceramic capacitor samples.
AgNbO to be measured 3 (x=6) silver niobate ceramic material in ceramic capacitor is of single perovskite structure; at room temperature, 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 3 The energy storage efficiency is 45%.
Example six:
as shown in fig. 1, 2, 4 and 5, a preparation method of a silver niobate ceramic capacitor with high energy storage comprises the following steps:
s1, high-purity Ag 2 O powder and Nb 2 O 5 Weighing the 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, wherein the ball milling rotating speed is 300 revolutions per minute, and after ball milling, placing the ball-milled mixture into an oven at 80 ℃ for drying for 12 hours; manually grinding the dried mixture for 40 minutes, and then pressing the mixture into a green body with the diameter of 20mm by adopting 200Mpa pressure;
s2, placing the green body in oxygen, presintering for 6 hours at 900 ℃, wherein the heating and cooling rates are 5 ℃/min, and preparing a rough blank;
s3, grinding the rough blank, sequentially performing ball milling and drying, and then adding a polyvinyl alcohol solution with the mass fraction of 5% for granulating, wherein the added mass of the polyvinyl alcohol solution is 5% of the mass of the powder; carrying out uniaxial compression 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 preserving heat for 6 hours, wherein the heating and cooling rates are 5 ℃/min, and preparing the ceramic wafer;
s5, grinding and polishing the ceramic wafer to a sheet with the thickness of 0.13mm, sequentially carrying out ultrasonic cleaning and drying, printing silver electrodes with the diameter of 2mm on two sides of the ceramic wafer in a screen printing mode, baking for 25min in a tubular furnace at 600 ℃, and naturally cooling to obtain AgNbO to be tested 3 (x=7) ceramic capacitor samples.
AgNbO to be measured 3 (x=7) silver niobate ceramic material in ceramic capacitor is of single perovskite structure; at room temperature, 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 3 The energy storage efficiency was 46%.
The following table shows the performance parameters of the energy storage ceramics prepared in examples 1-6 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/cm 3 | 46% |
The ceramic samples prepared in examples 1-6 were all of a single perovskite structure with no impurity phases present within the XRD accuracy. As shown in fig. 1, the (020) peak, the (220) peak, and the (008) peak are both shifted to high angles, indicating that the lattice parameter is reduced, and the unit cell volume becomes smaller, i.e., the lattice contracts, so that the antiferroelectric property of the system increases with the increase of pressure. As can be seen from fig. 2, as the sheeting pressure increases, the electric hysteresis loop becomes narrower, and the maximum breakdown field strength and the phase change 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, so the energy storage efficiency is higher. As can be seen from FIG. 5, the ceramic sample prepared in example 4 has the highest energy storage density, up to 4.8J/cm3, and the energy storage efficiency can reach 45%.
According to the invention, under the condition that other elements are not introduced, a new thought of mechanical constraint is adopted, and the structure of the silver niobate energy storage ceramic is optimized by regulating and controlling the uniaxial pressing pressure, so that the antiferroelectricity of the silver niobate energy storage ceramic is enhanced, and the lead-free energy storage ceramic with high energy storage density, high breakdown electric field and high polarization strength can be obtained.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (8)
1. A high energy storage silver niobate ceramic capacitor, characterized by: the silver niobate ceramic material in the silver niobate ceramic capacitor has a single perovskite structure; at room temperature, the energy storage density of the silver niobate ceramic material is 2.4J/cm 3 ～4.8J/cm 3 ；
The preparation method of the high energy storage silver niobate ceramic capacitor comprises the following steps:
ag with 2 O powder and Nb 2 O 5 Sequentially performing ball milling mixing, drying and tabletting on the powder to prepare a green body;
placing the green body in oxygen for presintering to obtain a rough blank;
grinding and crushing the rough blank, and then sequentially performing ball milling, drying, granulating and high-pressure uniaxial pressing and forming to obtain a biscuit; the uniaxial pressing pressure used in uniaxial pressing is 120xMPa, wherein 2 is less than or equal tox≤7；
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 sides of the ceramic sheet, calcining and cooling.
2. The high energy storage silver niobate ceramic capacitor of claim 1, wherein: at room temperature, the breakdown electric field of the silver niobate ceramic material is 175 kV/cm-342 kV/cm.
3. The high energy storage silver niobate ceramic capacitor of claim 1, wherein: at room temperature, the polarization strength of the silver niobate ceramic material is 33 mu C/cm 2 ~52μC/cm 2 。
4. The high energy storage silver niobate ceramic capacitor of claim 1, wherein: at room temperature, the energy storage efficiency of the silver niobate ceramic material is 42-46%.
5. The high energy storage silver niobate ceramic capacitor of claim 1, wherein: ag (silver) 2 O powder and Nb 2 O 5 Mixing the powder according to the mass ratio of 1:1, wherein the uniaxial tabletting pressure adopted in the tabletting process is 150 mpa-300 mpa in the process of preparing green bodies.
6. The high energy storage silver niobate ceramic capacitor of claim 1, wherein: during granulation, the selected adhesive is a polyvinyl alcohol solution with the mass fraction of 5%, and the addition amount of the adhesive is 4-6% of the mass of the powder.
7. The high energy storage silver niobate ceramic capacitor of claim 1, wherein: presintering for 4-6 hours at 850-950 ℃; discharging the adhesive for 2 hours at 600 ℃; sintering for 4-6 h at 1060-1080 ℃.
8. The high energy storage silver niobate ceramic capacitor of claim 1, wherein: the thickness of the ceramic sheet is 0.10 mm-0.20 mm; calcining for 20-30 min at 580-600 ℃.
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| JP2018008863A (en) * | 2016-07-11 | 2018-01-18 | 茂野 交市 | Dielectric ceramic material and dielectric ceramic composition |
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