CN115159976A - Method for improving energy storage density of copper strontium calcium titanate dielectric ceramic material - Google Patents
Method for improving energy storage density of copper strontium calcium titanate dielectric ceramic material Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 16
- MUSNICXQWHQDQB-UHFFFAOYSA-N [Cu][Ca][Sr] Chemical compound [Cu][Ca][Sr] MUSNICXQWHQDQB-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000011575 calcium Substances 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 12
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims abstract description 12
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
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- 238000001035 drying Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012700 ceramic precursor Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- -1 diisopropyl titanate Chemical compound 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000012856 weighed raw material Substances 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 1
- RINWGRJHXCCLOV-UHFFFAOYSA-N BPO Chemical compound BPO RINWGRJHXCCLOV-UHFFFAOYSA-N 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000197 pyrolysis Methods 0.000 abstract description 5
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 abstract description 3
- CSKRBHOAJUMOKJ-UHFFFAOYSA-N 3,4-diacetylhexane-2,5-dione Chemical compound CC(=O)C(C(C)=O)C(C(C)=O)C(C)=O CSKRBHOAJUMOKJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052729 chemical element Inorganic materials 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910004247 CaCu Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- PLZFHNWCKKPCMI-UHFFFAOYSA-N cadmium copper Chemical compound [Cu].[Cd] PLZFHNWCKKPCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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Abstract
The invention discloses a method for improving the energy storage density of a copper strontium calcium titanate dielectric ceramic material. The ceramic material has the composition of Ca 1‑ x Sr x Cu 3 Ti 4 O 12 (0<x<1). CSCTO powder is prepared by polymer pyrolysis method. The process comprises the following steps: copper nitrate, calcium nitrate, strontium nitrate and bis (acetylacetone) diisopropyl titanate are taken as raw materials, and the raw materials are weighed and proportioned according to the metering ratio of each chemical element; selecting proper polymer monomers and initiators; mixing the raw materials, placing the mixture in a water bath kettle, and continuously stirring the mixture until dry gel is formed; removing organic matters in the xerogel to form precursor powder; and then preparing a ceramic blank, sintering and cooling to obtain the CSCTO dielectric ceramic. The dielectric constant of the CSCTO ceramic is 698 under the conditions of room temperature and 1 kHz, the breakdown field strength is 717 kV/cm, the energy storage density is increased to 15.88J/cm < 3 >, the energy storage efficiency reaches 95 percent, and the energy storage device for preparing pulse power equipmentHas wide application prospect.
Description
Technical Field
The invention belongs to the technical field of dielectric ceramic synthesis application, and particularly relates to a method for improving the energy storage density of a copper strontium calcium titanate dielectric ceramic material.
Background
CaCu 3 Ti 4 O 12 The ceramic material (CCTO for short) is a new type dielectric ceramic with perovskite cubic crystal structure, has huge dielectric constant and keeps stable in a certain frequency and temperature. In addition, CCTO ceramics have good non-ohmic properties and mechanical properties, and these excellent properties fill their potential in electronic device miniaturization and energy storage applications. However, the practical application range is limited due to the low energy storage density. According to a linear medium energy storage density calculation formula: w =1/2 ε 0 ε r E b 2 (wherein ε r Is the relative dielectric constant, E b Is the breakdown field strength), increases epsilon r And E b W can be increased. At the present stage, researchers at home and abroad improve the general idea of w to optimize two parameters simultaneously. However, studies have shown that both are parameters that cannot be optimized simultaneously, making little use of the benefit of improving one party at the expense of the other.
At present, many research results at home and abroad show that: CCTO-based ceramic dielectrics have low energy storage densities, generally less than 0.006J/cm 3 (Li, Jianying, et al. "Towards enhanced varistor property and lower dielectric loss of CaCu 3 Ti 4 O 12 based ceramics." Materials &Design 92 (2016): 546-551.). Ca prepared by solid-phase reaction method 0.5 Sr 0.5 Cu 3 Ti 4 O 12 In the ceramic, the dielectric constant is reduced to about 1000, and the energy storage density is improved to 0.05J/cm 3 (Felix, A. A., et al. "Enhanced electrical behavior in Ca 1-x Sr x Cu 3 Ti 4 O 12 Ceramics. "Ceramics International 45.11 (2019): 14305-14311.). In addition, the dielectric constant of the zirconium titanate copper-cadmium material is 15032, the breakdown field strength is 1.5 kV/cm, and the energy storage density is 0.002J/cm 3 (a zirconium titanate copper cadmium giant dielectric ceramic material with high breakdown field strength and a preparation method thereof, CN 107216147B). Ca prepared by sol-gel method 0.5 Sr 0.5 Cu 3 Ti 4 O 12 The dielectric constant and the breakdown field strength of the dielectric ceramic are 3902 and 52.5 kV/cm respectively, and the energy storage density is improved to 0.5J/cm 3 (a high breakdown field strength copper strontium calcium titanate dielectric ceramic material and a preparation method thereof, CN 109553411B). From the current research situation, caCu 3 Ti 4 O 12 The energy storage density of ceramics is generally low, and the research on CCTO ceramic energy storage by domestic scholars is less.
Therefore, if the energy storage density of the CCTO ceramic can be successfully and greatly improved by changing the preparation method or the doping and replacing modes, the application range of the CCTO ceramic in practice can be further expanded, and particularly the CCTO ceramic has extremely important application value in the aspect of preparing pulse power devices.
Disclosure of Invention
Aiming at the technical problem of low energy storage density of CCTO products, the invention uses Ca 0.4 Sr 0.6 Cu 3 Ti 4 O 12 The (CSCTO) dielectric ceramic material is used as a carrier, and a method for improving the energy storage density of the ceramic material of the grain boundary layer is provided.
The technical scheme adopted by the invention for realizing the purpose is as follows:
（1） Ca 1-x Sr x Cu 3 Ti 4 O 12 preparation of ceramic precursor powder according to Ca 1-x Sr x Cu 3 Ti 4 O 12 Weighing raw materials of copper nitrate, calcium nitrate, strontium nitrate and bis (acetylacetone) diisopropyl titanate according to the stoichiometric ratio, selecting polymer monomers with proper concentration for the raw materials, and taking the monomers as copper nitrate, calcium nitrate, strontium nitrate and bis (acetylacetone) diisopropyl titanate1.5 to 2 times of the mole number of the metal cations in the bis (acetylacetonato) diisopropyl titanate; pouring the weighed raw materials into a polymer monomer solution, continuously stirring to fully dissolve and disperse the raw materials, and adding an initiator accounting for 0.5 percent of the mass of the polymerized monomer into the mixed solution after uniformly mixing to promote polymerization reaction; then putting the container containing the solution into a constant-temperature water bath kettle and stirring until gel is formed; after the gel is formed, setting the temperature of a water bath to be 85-90 ℃, and continuously preserving the heat for 10-12 h to ensure that the solvent is completely volatilized and the gel is sufficiently dried; putting the gel into an evaporation pan, removing organic matters from the gel by using an electric furnace, grinding the gel, putting the gel into a muffle furnace, and presintering the gel at a high temperature to form CSCTO ceramic precursor powder;
（2） Ca 1-x Sr x Cu 3 Ti 4 O 12 the preparation of the ceramic is that the precursor powder is poured into an agate mortar, 4-5 drops of PVA adhesive with the mass fraction of 5 percent are added into the precursor powder, and the mixture is stirred uniformly, ground fully, sieved, granulated and then put into an oven for proper drying; weighing a proper amount of the prepared powder, putting the powder into a grinding tool, and tabletting to obtain a CSCTO ceramic blank; putting the blank into a drying box, completely drying at 70-90 ℃, putting the blank into a muffle furnace, and carrying out heat preservation sintering to ensure that the crystal grains uniformly and completely grow; after sintering, naturally cooling to room temperature in a furnace to obtain Ca 1-x Sr x Cu 3 Ti 4 O 12 A dielectric ceramic. Finally, silver is plated on the surface of the sintered ceramic sample, and related performance measurement is carried out by using instruments such as X-ray diffraction, a broadband dielectric spectrometer, a high impedance meter and the like.
The invention provides a method for greatly reducing the energy storage density of CCTO ceramics r While obtaining an epsilon of moderate intensity r And E of moderate strength b Finally, a new idea of improving the energy storage density effect is achieved. In addition, compared with other ceramic powder preparation methods, the polymer pyrolysis method adopted by the invention can obtain finer grains, larger grain boundary density, better sample density and uniformity, and can improve E b Is more advantageous.
The invention adopts the polymer pyrolysis method to prepare C with similar structure and performance to CCTOThe SCTO dielectric ceramic has the advantages of simple preparation method operation, good repeatability, high yield, good sample uniformity and high densification degree, and the energy storage density of the prepared CSCTO dielectric ceramic can be greatly increased to 15.88J/cm 3 And has the characteristic of high energy storage density. The high energy storage density dielectric ceramic has very wide prospect in the application of pulse power energy storage.
Drawings
FIG. 1 Ca 0.4 Sr 0.6 Cu 3 Ti 4 O 12 XRD pattern of dielectric ceramic sample;
FIG. 2 Ca 0.4 Sr 0.6 Cu 3 Ti 4 O 12 A dielectric constant and dielectric loss spectrogram of the dielectric ceramic sample;
FIG. 3 Ca 0.4 Sr 0.6 Cu 3 Ti 4 O 12 J-E curves of the dielectric ceramic samples.
Detailed Description
The heat preservation sintering temperature of the blank in the step (2) is 1000 to 1100 ℃, and the sintering time is 10 to 12 hours; the polymer monomer in the step (1) is methanol or ethyl acetate or acrylic acid; in the step (1), the initiator is AIBN (azodiisobutyronitrile) or persulfate or BPO (dibenzoyl peroxide).
The present invention will be further described with reference to the following embodiments. The following description is merely exemplary in nature and is not intended to limit the scope of the present disclosure.
According to Ca 0.4 Sr 0.6 Cu 3 Ti 4 O 12 The chemical formula is that calcium nitrate, strontium nitrate, copper nitrate and bis (acetylacetone) diisopropyl titanate are weighed as 2.43 g, 3.21 g, 18.30 g and 48.56 g respectively. In addition, an appropriate amount of polymer monomer is weighed and dissolved in deionized water to form a solution of a certain concentration (as long as sufficient dissolution of the starting material is ensured). Then, the above raw materials were poured into a beaker containing the monomers, and were continuously stirred with a glass rod to be sufficiently dissolved, thereby forming a green mixed solution. Weighing a reaction initiator, dissolving the reaction initiator in deionized water to form a solution with a proper concentration, and pouring the solution into a green mixed solution to promote polymerization reactionAnd (4) generating. Then, the mixed solution is placed in a water bath kettle at the temperature of 80 ℃, the stirring rod is kept at 200 to 250 rpm for stirring to form gel, and then the temperature is raised to 85 ℃ and the heat is kept for 10 h to fully dry the gel. Pouring the xerogel into an evaporation dish, placing the evaporation dish on an electric furnace, and keeping the temperature of the electric furnace to be 400-500 ℃ to remove organic matters in the gel; and then placing the ceramic powder into a muffle furnace for high-temperature presintering at 850 ℃ to form CSCTO ceramic precursor powder.
Placing CSCTO ceramic precursor powder into an agate mortar to be ground to a proper particle size, adding 5 mass percent of PVA (polyvinyl alcohol) adhesive into the precursor powder, and drying in an oven for 20 min; 0.3 g powder is weighed and put into a die, and is pressed into round pieces with the diameter of 3 cm and the thickness of 1 mm by the pressure of 100 MPa. And (3) putting the pressed blank body into an oven to be dried for 12 h, then putting the dried blank body into a muffle furnace, raising the temperature to 350 ℃ at the heating rate of 8 ℃/min to perform drying and dehumidification, then heating to 850 ℃ at the same heating rate to perform heat preservation for 30 min to perform glue discharging, and finally raising the temperature to 1010 ℃ at the heating rate of 5 ℃/min to perform heat preservation for 10 h to perform sintering. And after sintering, naturally cooling the sample to room temperature in the air to obtain the CSCTO ceramic. And uniformly coating silver paste on the surface of the sintered CSCTO ceramic sample, preserving the temperature in a muffle furnace at 650 ℃ for 30 min to finish silver plating, and then measuring the dielectric property. The measured dielectric constant of the CSCTO ceramic material with high energy storage density is 698, the breakdown field intensity is 717 kV/cm, and the energy storage density is greatly increased to 15.88J/cm 3 . As shown in table 1.
Compared with the work of other researchers, the sample performances listed in the table 1 show that the effect of simultaneously improving the dielectric constant and the breakdown field strength of the CCTO-based dielectric ceramic by a sol-gel method or a polymer pyrolysis method on the improvement of the energy storage density is not obvious, and from the change trend of the breakdown field strength and the dielectric constant, the experience that the two have a competitive relationship is verified again. According to a linear medium energy storage density calculation formula, the effect of breakdown field intensity on improving the energy storage density is more obvious, so that the CCTO ceramic epsilon is greatly reduced r While obtaining an epsilon of moderate intensity r And E of moderate strength b Finally achieving a new idea of improving the energy storage density effect and successfully carrying out the pyrolysis method of the polymer to the CCTO-based dielectric ceramicThe energy storage density is increased to a new height. It can be seen that the proposed concept has outstanding substantive features and significant effects compared with previous concepts.
Claims (5)
1. A method for improving the energy storage density of a copper strontium calcium titanate dielectric ceramic material is characterized by comprising the following steps:
（1） Ca 1-x Sr x Cu 3 Ti 4 O 12 and (3) preparing ceramic precursor powder. According to Ca 1-x Sr x Cu 3 Ti 4 O 12 Weighing raw materials such as copper nitrate, calcium nitrate, strontium nitrate, bis (acetylacetonato) diisopropyl titanate and the like according to the stoichiometric ratio, selecting a polymer monomer with a proper concentration for the raw materials, wherein the amount of the monomer is 1.5 to 2 times of the mole number of metal cations in the copper nitrate, the calcium nitrate, the strontium nitrate and the bis (acetylacetonato) diisopropyl titanate; pouring the weighed raw materials into a polymer monomer solution, continuously stirring to fully dissolve and disperse the raw materials, and adding an initiator accounting for 0.5 percent of the mass of the polymer monomer into the mixed solution after uniformly mixing to promote polymerization reaction; then putting the container containing the solution into a constant-temperature water bath kettle and stirring until gel is formed; after the gel is formed, setting the temperature of a water bath kettle to be 85 to 90 ℃, and continuously preserving the heat for 10 to 12 hours to ensure that the solvent is completely volatilized and the gel is sufficiently dried; putting the gel into an evaporating dish, removing organic matters by using an electric furnace, grinding, putting into a muffle furnace, and presintering at high temperature to form CSCTO ceramic precursor powder;
（2） Ca 1-x Sr x Cu 3 Ti 4 O 12 and (3) preparing the ceramic. Pouring the precursor powder into an agate mortar, adding 4-5 drops of 5% PVA (polyvinyl alcohol) adhesive into the precursor powder, uniformly stirring, fully grinding, sieving, granulating and then putting into an oven for proper drying; weighing appropriate amount of the obtained powder, placing into a grinding tool, and tabletting to obtain CSCTO ceramic green body; putting the blank into a drying box, completely drying at 70-90 ℃, putting the blank into a muffle furnace, and carrying out heat preservation sintering to ensure that the crystal grains uniformly and completely grow; after sintering, naturally cooling to room temperature in a furnace to obtain Ca 1-x Sr x Cu 3 Ti 4 O 12 A dielectric ceramic.
2. The method for improving the energy storage density of the copper strontium calcium titanate dielectric ceramic material according to claim 1, wherein the container containing the solution in the step (1) is placed in a constant-temperature water bath kettle, and the temperature is 70 to 80 ℃ to form sol; and (3) presintering the mixture in a muffle furnace at a high temperature of 800-850 ℃.
3. The method for improving the energy storage density of the copper strontium calcium titanate dielectric ceramic material according to claim 1 or 2, wherein the temperature of the green body in the step (2) is 1000 to 1100 ℃, and the sintering time is 10 to 12 hours.
4. The method for improving the energy storage density of the copper strontium calcium titanate dielectric ceramic material according to claim 1 or 2, wherein the polymer monomer in the step (1) is methanol or ethyl acetate or acrylic acid.
5. The method for improving the energy storage density of the copper strontium calcium titanate dielectric ceramic material according to claim 1 or 2, wherein the initiator in step (1) is AIBN or persulfate or BPO.
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Application publication date: 20221011 |