CN115974548B - Leadless high-entropy ferroelectric film, preparation method and application thereof - Google Patents
Leadless high-entropy ferroelectric film, preparation method and application thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 claims abstract description 59
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- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000011734 sodium Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 17
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 16
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 14
- 230000005684 electric field Effects 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 13
- 229960000583 acetic acid Drugs 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012362 glacial acetic acid Substances 0.000 claims description 12
- 238000004528 spin coating Methods 0.000 claims description 12
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 8
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims description 8
- 235000011056 potassium acetate Nutrition 0.000 claims description 8
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- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 8
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 8
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 150000001621 bismuth Chemical class 0.000 claims description 6
- 150000002603 lanthanum Chemical class 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 159000000008 strontium salts Chemical class 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
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- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
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- Inorganic Insulating Materials (AREA)
Abstract
The application belongs to the technical field of film materials, and discloses a lead-free high-entropy ferroelectric film, a preparation method and application thereof. The application prepares the lead-free high-entropy ferroelectric film with controllable thickness by using a sol-gel method, and the sol-gel method has the advantages of simple process, low equipment requirement, low production cost and good film forming efficiency and uniformity, and is applicable to large-area film making; the proportion of the material prepared by the sol-gel method to the chemical components is easy to control, and the material can be designed by molecular structure engineering, so that the method is particularly suitable for preparing lead-free high-entropy ferroelectric film multicomponent materials. The lead-free high-entropy ferroelectric film prepared by the application has ultrahigh breakdown field strength and good temperature stability, the breakdown field strength which can be born by the film can be more than 8MV/cm, and the energy storage density can reach 5.88J/cm 3 The energy storage efficiency can reach 93%, can work normally under the condition of-55-200 ℃, and has larger dielectric constant and smaller dielectric loss.
Description
Technical Field
The application belongs to the technical field of film materials, and particularly relates to a lead-free high-entropy ferroelectric film, and a preparation method and application thereof.
Background
At present, researches have reported that the breakdown electric field strength of a common ferroelectric film is generally 1-2MV/cm (reference 1:Xie,Yanjiang,et al. "Ultra-high Energy storage density and enhanced dielectric properties in BNT-BT based thin film." Ceramics International 47.16 (2021): 23259-23266; reference 2:Peng,Biaolin,et al. "Low-temperature-poling awakened high dielectric breakdown strength and outstanding improvement of discharge Energy density of (Pb, la) (Zr, sn, ti) O3 relay thin film." Nano Energy 77 (2020): 105132), the breakdown electric field strength of a commercial polymer film is 0.2-0.6MV/cm (reference 3: pei, jia-Yao, et al. "Enhancement of breakdown strength of multilayer polymer film through electric field redistribution and defect modification." Applied Physics Letters 114.10 (2019): 103702; reference 4:Samant,Saumil P. "direct-assembly of block copolymers for high breakdown strength polymer film capacitors)," ACS applied materials & internal 8.12 (wear) 7966-7976), the breakdown electric field strength of a ceramic particle/polymer composite film is 2.3-4.6 MV/cm (reference 3: pei, jia-Yao, et al. "Enhancement of breakdown strength of multilayer polymer film through electric field redistribution and defect modification." Applied Physics Letters 114.10 (2019): 103702; reference 4:Samant,Saumil P. "direct-assembly of block copolymers for high breakdown strength polymer film capacitors)," ACS applied materials & internal 8.12 (wear): 7966-7976), and the breakdown electric field strength of a ceramic particle/polymer composite film is 2.3-6.6/cm (reference 3: brif-6958); brif-37 (wear 6) ("Brif." 37:37), "Compositional tailoring effect on electric field distribution for significantly enhanced breakdown strength and restrained conductive loss in sandwich-structured ceramic/Polymer nanocomposites", "Journal of Materials Chemistry A5.9.9 (2017): 4710-4718). The breakdown field strength of the film materials is low, and the requirements of the market for higher breakdown field strength (more than 5 MV/cm) cannot be met.
The high-entropy ferroelectric material is a solid solution compound formed by more than 4 metal elements at a certain point in a crystal structure of the material according to an equimolar ratio or an approximately equimolar ratio, and is characterized in that the enhancement of chemical disorder maximizes configuration entropy, so that a more stable system is realized. Compared with the traditional ferroelectric material, the high-entropy ferroelectric material has stable thermodynamic phase, obvious lattice distortion, ingredient complexity and other inherent characteristics. These properties enable the high-entropy ferroelectric material to have good thermal stability, stronger mechanical properties, outstanding piezoelectric properties and dielectric properties.
The traditional preparation of the high-entropy ferroelectric material generally adopts a physical solid-phase reaction method, but the method is suitable for preparing corresponding bulk materials and is not suitable for preparing the high-entropy ferroelectric film. The ferroelectric thin film material is generally prepared by Physical Vapor Deposition (PVD) and Chemical Vapor Deposition (CVD). PVD is to gasify metal and deposit the metal on a substrate through interatomic collision under a vacuum high-temperature environment to form a film, but the method has high requirement on vacuum degree. For the multi-component compound, the melting point and vapor pressure among elements are strictly required, and meanwhile, the component proportion control degree is small, and the film forming is uneven and has poor quality. CVD is a process of forming a thin film on a substrate by chemical reaction deposition using various vapor phase materials at high temperatures. However, this method has a great limitation, for example, toxic reaction gas generated during the preparation process, some reaction products (impurities) may remain in the coating film, the high temperature resistance of the substrate is good (> 1000 ℃) and the preparation cost is high.
Therefore, how to overcome the problems of high equipment requirement and high cost of the preparation method of the high-entropy ferroelectric film and develop the high-entropy ferroelectric film with higher breakdown field strength become urgent demands of the current electronic industry.
Disclosure of Invention
The present application aims to solve at least one of the technical problems in the prior art described above. Therefore, the application provides a preparation method of a lead-free high-entropy ferroelectric film, which utilizes a sol-gel method to prepare the lead-free high-entropy ferroelectric film with controllable thickness, has low equipment requirement and low cost, and the prepared lead-free high-entropy ferroelectric film has ultrahigh breakdown electric field strength, and the breakdown electric field strength of the lead-free high-entropy ferroelectric film is more than 8MV/cm.
The first aspect of the application provides a preparation method of a lead-free high-entropy ferroelectric film, which comprises the following steps:
1) Preparing BNKLST precursor solution, wherein the BNKLST has a chemical formula (Bi x Na x K y La y Sr y )TiO 3 Where x > 0, y > 0, 2x+3y=1;
2) Spin-coating the BNKLST precursor solution obtained in the step 1) on a conductive substrate to obtain a wet film;
3) Drying the wet film obtained in the step 2) at 200-250 ℃ for 3-5min, and then pyrolyzing at 400-450 ℃ for 3-5min to obtain an amorphous film;
4) Carrying out rapid heating treatment on the amorphous film obtained in the step 3); the rapid heating treatment is as follows: heating to 650-700 deg.C at a heating rate of 50-100deg.C/s, and maintaining for 3-5min;
5) And 4) annealing the amorphous film subjected to the rapid heating treatment in the step 4) to obtain the lead-free high-entropy ferroelectric film.
Preferably, the preparation of the BNKLST precursor solution in step 1) is performed in particular as follows:
weighing bismuth salt, sodium salt, potassium salt, strontium salt, lanthanum salt and titanium salt according to the stoichiometric ratio of the chemical formula;
dissolving the bismuth salt in a solvent, and then adding the sodium salt, the potassium salt, the strontium salt and the lanthanum salt, and dissolving to obtain a solution A;
mixing the titanium salt with a solvent and a chelating agent to obtain a solution B;
adding the solution B into the solution A, adding formamide with the volume ratio of 0.5-1%, stirring for 24-36h, standing for 72-84h, and reacting to obtain the BNKLST precursor solution.
Preferably, the bismuth salt includes at least one of bismuth acetate, bismuth nitrate and bismuth sulfate; the sodium salt comprises at least one of sodium acetate trihydrate, sodium nitrate and sodium sulfate; the potassium salt comprises at least one of potassium acetate, potassium nitrate and potassium sulfate; the strontium salt comprises at least one of strontium acetate, strontium nitrate and strontium sulfate; the lanthanum salt comprises at least one of lanthanum nitrate hexahydrate, lanthanum nitrate and lanthanum sulfate; the titanium salt is tetrabutyl titanate.
Preferably, the solvent comprises at least one of glacial acetic acid, ethylene glycol methyl ether, ethanol and isopropanol; the chelating agent comprises at least one of acetylacetone, EDTA, potassium sodium tartrate and ammonium citrate.
Preferably, the ratio of x to y is 0.5-2:1.
Preferably, the annealing conditions include: the annealing temperature is 650-700 ℃, and the annealing time is 10-15min.
Preferably, steps 2), 3) and 4) are repeated a plurality of times before said step 5) is performed, resulting in a multilayer amorphous film.
Preferably, the number of layers of the lead-free high-entropy ferroelectric film is 4-10, and the thickness of each layer of the lead-free high-entropy ferroelectric film is 40-50nm.
The second aspect of the application provides a lead-free high-entropy ferroelectric film, which is prepared by the preparation method of the application, and the breakdown electric field strength of the lead-free high-entropy ferroelectric film is more than 8MV/cm.
Preferably, the lead-free high-entropy ferroelectric thin film is a single-phase crystal structure.
A third aspect of the application provides a dielectric energy storage device comprising a lead-free high-entropy ferroelectric thin film according to the application.
Compared with the prior art, the application has the following beneficial effects:
(1) The preparation method of the lead-free high-entropy ferroelectric film has the advantages of simple process, low equipment requirement, low production cost and good film forming efficiency and uniformity, and is applicable to large-area film making by using a sol-gel method to prepare the lead-free high-entropy ferroelectric film with controllable thickness; the proportion of the material prepared by the sol-gel method to the chemical components is easy to control, and the material can be designed by molecular structure engineering, so that the method is particularly suitable for preparing lead-free high-entropy ferroelectric film multicomponent materials.
(2) The lead-free high-entropy ferroelectric film prepared by the application has ultrahigh breakdown field strength and good temperature stability, the breakdown field strength which can be born is more than 8MV/cm, and the energy storage density can reach 5.88J/cm 3 The energy storage efficiency can reach 93%, can work normally under the condition of-55-200 ℃, and has larger dielectric constant and smaller dielectric loss.
(3) The lead-free high-entropy ferroelectric film prepared by the method does not contain toxic elements such as lead, and is more environment-friendly than a lead-containing ferroelectric film; the dielectric energy storage device prepared by the lead-free high-entropy ferroelectric film has excellent energy storage density and energy storage efficiency.
Drawings
FIG. 1 is an XRD pattern of a lead-free high-entropy ferroelectric thin film obtained in example 1;
FIG. 2 is a SEM image of the cross section of a lead-free high-entropy ferroelectric film obtained in example 1;
FIG. 3 is a graph of dielectric constant and dielectric loss as a function of frequency for the dielectric energy storage device assembled from example 1;
FIG. 4 is a graph of electrical conductivity versus temperature for the dielectric energy storage device assembled in accordance with example 1;
FIG. 5 is a weber distribution plot of the breakdown electric field of the dielectric energy storage device assembled in example 1;
FIG. 6 is a graph of the hysteresis loop of the dielectric energy storage device assembled from example 1;
fig. 7 is an SEM image of a cross section of the lead-free high-entropy ferroelectric thin film obtained in comparative example 1;
fig. 8 is a graph of the hysteresis loop of the dielectric energy storage device assembled from comparative example 1.
Detailed Description
In order to make the technical solutions of the present application more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the application.
The starting materials, reagents, apparatus used in the examples below were obtained from conventional commercial sources, unless otherwise specified, or may be obtained by methods known in the art.
The room temperature in the application is 25+/-5 ℃; slowly dropping means that the dropping rate is 5-10 seconds/drop; slow stirring means a stirring rate of 10-20rpm; amorphous films refer to films in which the amorphous state has not yet crystallized.
Example 1
The preparation method of the lead-free high-entropy ferroelectric film comprises the following steps:
1) Preparation (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Precursor solution:
according to (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Weighing bismuth acetate, sodium acetate trihydrate, potassium acetate, strontium acetate, lanthanum nitrate hexahydrate and tetrabutyl titanate as raw materials according to stoichiometric ratio, adding bismuth acetate into a proper amount of glacial acetic acid, heating and stirring for 30min at 70 ℃, adding a small amount of deionized water and stirring for 30min, and then sequentially adding sodium acetate trihydrate, potassium acetate, strontium acetate and tetrabutyl titanateLanthanum nitrate hexahydrate is stirred for 2.5 hours and dissolved to obtain solution A;
mixing three solutions of tetrabutyl titanate, ethylene glycol methyl ether and acetylacetone according to the volume ratio of 1:3:2 at room temperature, and stirring for 1h to obtain a solution B;
heating the solution A to 80 ℃, slowly dripping the solution B into the solution A, adding a proper amount of 0.2M glacial acetic acid after the solution B is completely added, stirring for 3 hours, adding formamide with the volume ratio of 0.5%, slowly stirring for 24 hours at room temperature, standing for 72 hours, and reacting to obtain (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 A precursor solution;
2) Pt (111)/Ti/SiO at 1cm×1cm 2 5 drops (Bi) were dropped on the Si (100) conductive substrate 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Spin-coating the precursor solution for 9s at a rotating speed of 600r/min by using a spin coater, and spin-coating for 30s at a rotating speed of 3000r/min to obtain a wet film;
3) Placing the wet film on an electric heating flat plate, drying for 5min at 200 ℃, and then pyrolyzing for 5min at 400 ℃ to obtain an amorphous film;
4) Subjecting the amorphous film to a rapid heat treatment; the rapid heating treatment is as follows: heating the amorphous film to 650 ℃ by adopting a rapid annealing furnace at a heating rate of 80 ℃/s, and preserving heat for 5min;
5) Repeating the steps 2), 3) and 4) for 3 times, and then carrying out annealing treatment for 15min at 650 ℃ to obtain 4 layers of lead-free high-entropy ferroelectric film.
Product characterization:
1. the lead-free high-entropy ferroelectric film obtained in example 1 was subjected to X-ray diffraction, and the XRD pattern thereof was shown in fig. 1. It can be seen from fig. 1 that the lead-free high-entropy ferroelectric thin film of the present application exhibits a perovskite crystal structure, and is free from impurity phases and impurities.
2. The cross section of the lead-free high-entropy ferroelectric film obtained in example 1 was subjected to SEM electron microscope scanning, and the SEM image thereof is shown in fig. 2. From top to bottom in FIG. 2, "1" represents the scanning electron microscope sample stage background, "2"Representation (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 "3" means the Pt/Ti electrode layer of the conductive substrate and "4" means the SiO of the conductive substrate 2 A Si layer. From fig. 2, it can be seen that the lead-free high-entropy ferroelectric film of the present application has higher crystallinity and denser structure.
Product performance test:
the lead-free high-entropy ferroelectric film obtained in the embodiment 1 is used as a dielectric material to be assembled into a dielectric energy storage device. The conductive substrate of the lead-free high-entropy ferroelectric film is used as one electrode of a dielectric energy storage device, the other electrode of the dielectric energy storage device is prepared by depositing gold on the other surface of the lead-free high-entropy ferroelectric film through magnetron sputtering, and the diameter of the gold electrode is 0.4mm and the thickness of the gold electrode is 0.25 mu m. Performing relevant electrical performance tests on the assembled dielectric energy storage device;
as shown in FIG. 3, the test frequency ranges from 1 to 10 5 kHz. At a test frequency of 10kHz, the dielectric constant of the dielectric energy storage device is higher than 100 while the dielectric loss is lower than 0.05.
As shown in FIG. 4, the test voltage was 150V and the conductivity of the dielectric energy storage device at room temperature was 5.13×10 -4 S/m, leakage current of about 10 -7 A. At the same time, the conductivity can be stably maintained at 3.3X10 at the temperature of 60-140 DEG C -3 S/m。
As shown in fig. 5, the breakdown electric field strength Eb of the dielectric energy storage device was measured according to weber distribution, and was eb=10.99 MV/cm. The dielectric energy storage device obtains higher energy storage effect with ultrahigh breakdown electric field strength.
As shown in FIG. 6, the dielectric energy storage device is subjected to hysteresis loop test under the condition of periodic triangular wave signal with the frequency of 1000Hz and the maximum voltage of 95V, and 5.88J/cm of dielectric energy storage device can be obtained 3 And an excellent energy storage efficiency of 93%.
Comparative example 1 (the difference from example 1 is that the amorphous film was subjected to conventional heat treatment)
The preparation method of the lead-free high-entropy ferroelectric film comprises the following steps:
1) Preparation (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Precursor solution:
according to (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Weighing bismuth acetate, sodium acetate trihydrate, potassium acetate, strontium acetate, lanthanum nitrate hexahydrate and tetrabutyl titanate as raw materials according to the stoichiometric ratio, adding bismuth acetate into a proper amount of glacial acetic acid, heating and stirring for 30min at 70 ℃, adding a small amount of deionized water and stirring for 30min, then sequentially adding sodium acetate trihydrate, potassium acetate, strontium acetate and lanthanum nitrate hexahydrate, stirring for 2.5h, and dissolving to obtain a solution A;
mixing three solutions of tetrabutyl titanate, ethylene glycol methyl ether and acetylacetone according to the volume ratio of 1:3:2 at room temperature, and stirring for 1h to obtain a solution B;
heating the solution A to 80 ℃, slowly dripping the solution B into the solution A, adding a proper amount of 0.2M glacial acetic acid after the solution B is completely added, stirring for 3 hours, adding formamide with the volume ratio of 0.5%, slowly stirring for 24 hours at room temperature, standing for 72 hours, and reacting to obtain (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 A precursor solution;
2) Pt (111)/Ti/SiO at 1cm×1cm 2 5 drops (Bi) were dropped on the Si (100) conductive substrate 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Spin-coating the precursor solution for 9s at a rotating speed of 600r/min by using a spin coater, and spin-coating for 30s at a rotating speed of 3000r/min to obtain a wet film;
3) Placing the wet film on an electric heating flat plate, drying for 5min at 200 ℃, and then pyrolyzing for 5min at 400 ℃ to obtain an amorphous film;
4) Subjecting the amorphous film to conventional heat treatment; the conventional heat treatment is as follows: heating the amorphous film to 650 ℃ by a muffle furnace at a heating rate of 30 ℃/min, and preserving heat for 5min;
5) Repeating the steps 2), 3) and 4) for 3 times, and then carrying out annealing treatment for 15min at 650 ℃ to obtain 4 layers of lead-free high-entropy ferroelectric film.
The cross section of the lead-free high-entropy ferroelectric film obtained in comparative example 1 was subjected to electron microscopy, and the SEM image thereof is shown in fig. 7. In FIG. 7, from top to bottom, "1" indicates the background of the sample stage of the scanning electron microscope, "2" indicates (Bi 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 "3" means the Pt/Ti electrode layer of the conductive substrate and "4" means the SiO of the conductive substrate 2 A Si layer. From fig. 7, it can be seen that the lead-free high-entropy ferroelectric thin film of comparative example 1 is inferior in crystallinity and loose in structure.
The lead-free high-entropy ferroelectric film obtained in comparative example 1 is used as a dielectric material to be assembled into a dielectric energy storage device. The conductive substrate of the lead-free high-entropy ferroelectric film is used as one electrode of a dielectric energy storage device, the other electrode of the dielectric energy storage device is prepared by depositing gold on the other surface of the lead-free high-entropy ferroelectric film through magnetron sputtering, and the diameter of the gold electrode is 0.4mm and the thickness of the gold electrode is 0.25 mu m. The assembled dielectric energy storage device was subjected to a related electrical performance test (test conditions were the same as those in example 1). As shown in FIG. 8, the dielectric energy storage device has an energy storage density of at most 0.61J/cm under the same test conditions 3 The energy storage density of the dielectric energy storage device assembled in example 1 is significantly lower.
Example 2
The preparation method of the lead-free high-entropy ferroelectric film comprises the following steps:
1) Preparation (Bi) 0.26 Na 0.26 K 0.16 La 0.16 Sr 0.16 )TiO 3 Precursor solution:
according to (Bi) 0.26 Na 0.26 K 0.16 La 0.16 Sr 0.16 )TiO 3 Weighing bismuth acetate, sodium acetate trihydrate, potassium acetate, strontium acetate, lanthanum nitrate hexahydrate and tetrabutyl titanate as raw materials according to the stoichiometric ratio, adding bismuth acetate into a proper amount of glacial acetic acid, heating and stirring for 30min at 70 ℃, adding a small amount of deionized water and stirring for 30min, then sequentially adding sodium acetate trihydrate, potassium acetate, strontium acetate and lanthanum nitrate hexahydrate, stirring for 3h, and dissolving to obtain a solution A;
mixing three solutions of tetrabutyl titanate, ethylene glycol methyl ether and acetylacetone according to the volume ratio of 1:3:2 at room temperature, and stirring for 1h to obtain a solution B;
heating the solution A to 80 ℃, slowly dripping the solution B into the solution A, adding a proper amount of 0.2M glacial acetic acid after the solution B is completely added, stirring for 3 hours, adding formamide with the volume ratio of 0.5%, slowly stirring for 24 hours at room temperature, standing for 72 hours, and reacting to obtain (Bi) 0.26 Na 0.26 K 0.16 La 0.16 Sr 0.16 )TiO 3 A precursor solution;
2) Pt (111)/Ti/SiO at 1cm×1cm 2 5 drops (Bi) were dropped on the Si (100) conductive substrate 0.26 Na 0.26 K 0.16 La 0.16 Sr 0.16 )TiO 3 Spin-coating the precursor solution for 9s at a rotating speed of 600r/min by using a spin coater, and spin-coating for 30s at a rotating speed of 3000r/min to obtain a wet film;
3) Placing the wet film on an electric heating flat plate, drying for 5min at 200 ℃, and then pyrolyzing for 5min at 400 ℃ to obtain an amorphous film;
4) Subjecting the amorphous film to a rapid heat treatment; the rapid heating treatment is as follows: heating the amorphous film to 650 ℃ by adopting a rapid annealing furnace at a heating rate of 80 ℃/s, and preserving heat for 5min;
5) Repeating the steps 2), 3) and 4) for 3 times, and then carrying out annealing treatment for 15min at 650 ℃ to obtain 4 layers of lead-free high-entropy ferroelectric film.
The lead-free high-entropy ferroelectric film obtained in example 2 was used as a dielectric material to assemble a dielectric energy storage device. The conductive substrate of the lead-free high-entropy ferroelectric film is used as one electrode of a dielectric energy storage device, the other electrode of the dielectric energy storage device is prepared by depositing gold on the other surface of the lead-free high-entropy ferroelectric film through magnetron sputtering, and the diameter of the gold electrode is 0.4mm and the thickness of the gold electrode is 0.25 mu m. The dielectric energy storage device thus assembled was subjected to a dielectric energy storage performance test (the test conditions were the same as those in example 1), and the energy storage density of the dielectric energy storage device was measured to be 5.6J/cm 3 And energy storage efficiency 90%.
Example 3
The preparation method of the lead-free high-entropy ferroelectric film comprises the following steps:
1) Preparation (Bi) 1/4 Na 1/4 K 1/6 La 1/6 Sr 1/6 )TiO 3 Precursor solution:
according to (Bi) 1/4 Na 1/4 K 1/6 La 1/6 Sr 1/6 )TiO 3 Weighing bismuth nitrate, sodium nitrate, potassium nitrate, strontium nitrate, lanthanum nitrate and tetrabutyl titanate as raw materials, adding bismuth nitrate into a proper amount of glacial acetic acid, heating and stirring for 30min at 60 ℃, adding a small amount of deionized water and stirring for 30min, then sequentially adding sodium nitrate, potassium nitrate, strontium nitrate and lanthanum nitrate, stirring for 2h, and dissolving to obtain a solution A;
mixing three solutions of tetrabutyl titanate, ethylene glycol methyl ether and acetylacetone according to the volume ratio of 1:3:2 at room temperature, and stirring for 1h to obtain a solution B;
heating the solution A to 80 ℃, slowly dripping the solution B into the solution A, adding a proper amount of 0.2M glacial acetic acid after the solution B is completely added, stirring for 3 hours, adding formamide with the volume ratio of 0.5%, slowly stirring for 24 hours at room temperature, standing for 72 hours, and reacting to obtain (Bi) 1/4 Na 1/4 K 1/6 La 1/6 Sr 1/6 )TiO 3 A precursor solution;
2) Pt (111)/Ti/SiO at 1cm×1cm 2 5 drops (Bi) were dropped on the Si (100) conductive substrate 1/4 Na 1/4 K 1/ 6 La 1/6 Sr 1/6 )TiO 3 Spin-coating the precursor solution for 9s at a rotating speed of 600r/min by using a spin coater, and spin-coating for 30s at a rotating speed of 3000r/min to obtain a wet film;
3) Placing the wet film on an electric heating flat plate, drying for 5min at 200 ℃, and then pyrolyzing for 5min at 400 ℃ to obtain an amorphous film;
4) Subjecting the amorphous film to a rapid heat treatment; the rapid heating treatment is as follows: heating the amorphous film to 650 ℃ by adopting a rapid annealing furnace at a heating rate of 50 ℃/s, and preserving heat for 3min;
5) Repeating the steps 2), 3) and 4) for 5 times, and then carrying out annealing treatment for 15min at 650 ℃ to obtain 6 layers of lead-free high-entropy ferroelectric film.
The lead-free high-entropy ferroelectric film obtained in example 3 is used as a dielectric material to be assembled into a dielectric energy storage device. The conductive substrate of the lead-free high-entropy ferroelectric film is used as one electrode of a dielectric energy storage device, the other electrode of the dielectric energy storage device is prepared by depositing gold on the other surface of the lead-free high-entropy ferroelectric film through magnetron sputtering, and the diameter of the gold electrode is 0.4mm and the thickness of the gold electrode is 0.25 mu m. The dielectric energy storage device thus assembled was subjected to a dielectric energy storage performance test (the test conditions were the same as those in example 1), and the energy storage density of the dielectric energy storage device was measured to be 5.63J/cm 3 And 91% of energy storage efficiency.
Example 4
The preparation method of the lead-free high-entropy ferroelectric film comprises the following steps:
1) Preparation (Bi) 2/7 Na 2/7 K 1/7 La 1/7 Sr 1/7 )TiO 3 Precursor solution:
according to (Bi) 2/7 Na 2/7 K 1/7 La 1/7 Sr 1/7 )TiO 3 Weighing bismuth sulfate, sodium sulfate, potassium sulfate, strontium sulfate, lanthanum sulfate and tetrabutyl titanate as raw materials, adding bismuth sulfate into a proper amount of glacial acetic acid, heating and stirring for 30min at 80 ℃, adding a small amount of deionized water and stirring for 30min, then sequentially adding sodium sulfate, potassium sulfate, strontium sulfate and lanthanum sulfate, stirring for 3h, and dissolving to obtain a solution A;
mixing three solutions of tetrabutyl titanate, ethylene glycol methyl ether and acetylacetone according to the volume ratio of 1:3:2 at room temperature, and stirring for 1h to obtain a solution B;
heating solution A to 80deg.C, slowly dripping solution B into solution A, adding appropriate amount of 0.2M glacial acetic acid after completely adding solution B, stirring for 3 hr, adding formamide with volume ratio of 1%, and slowly stirring at room temperatureStirring for 24h, standing for 72h, and reacting to obtain (Bi 2/7 Na 2/7 K 1/7 La 1/7 Sr 1/7 )TiO 3 A precursor solution;
2) Pt (111)/Ti/SiO at 1cm×1cm 2 Dropwise adding 4 drops (Bi) on a Si (100) conductive substrate 2/7 Na 2/7 K 1/ 7 La 1/7 Sr 1/7 )TiO 3 Spin-coating the precursor solution for 9s at a rotating speed of 600r/min by using a spin coater, and spin-coating for 30s at a rotating speed of 3000r/min to obtain a wet film;
3) Placing the wet film on an electric heating flat plate, drying for 3min at 250 ℃, and then pyrolyzing for 3min at 450 ℃ to obtain an amorphous film;
4) Subjecting the amorphous film to a rapid heat treatment; the rapid heating treatment is as follows: heating the amorphous film to 700 ℃ by adopting a rapid annealing furnace at a heating rate of 100 ℃/s, and preserving the heat for 4min;
5) Repeating the steps 2), 3) and 4) for 9 times, and then carrying out annealing treatment for 10 minutes at 700 ℃ to obtain 10 layers of lead-free high-entropy ferroelectric film.
The lead-free high-entropy ferroelectric film obtained in example 4 was used as a dielectric material to assemble a dielectric energy storage device. The conductive substrate of the lead-free high-entropy ferroelectric film is used as one electrode of a dielectric energy storage device, the other electrode of the dielectric energy storage device is prepared by depositing gold on the other surface of the lead-free high-entropy ferroelectric film through magnetron sputtering, and the diameter of the gold electrode is 0.4mm and the thickness of the gold electrode is 0.25 mu m. The dielectric energy storage device thus assembled was subjected to a dielectric energy storage performance test (the test conditions were the same as those in example 1), and the energy storage density of the dielectric energy storage device was measured to be 5.87J/cm 3 And energy storage efficiency 90%.
While the preferred embodiment of the present application has been described in detail, the application is not limited to the embodiments, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the application, and these modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.
Claims (7)
1. The preparation method of the lead-free high-entropy ferroelectric film is characterized by comprising the following steps of:
1) Preparing BNKLST precursor solution, wherein the BNKLST has a chemical formula (Bi x Na x K y La y Sr y )TiO 3 Where x > 0, y > 0, 2x+3y=1;
2) Spin-coating the BNKLST precursor solution obtained in the step 1) on a conductive substrate to obtain a wet film;
3) Drying the wet film obtained in the step 2) at 200-250 ℃ for 3-5min, and then pyrolyzing at 400-450 ℃ for 3-5min to obtain an amorphous film;
4) Carrying out rapid heating treatment on the amorphous film obtained in the step 3); the rapid heating treatment is as follows: heating to 650-700 deg.C at a heating rate of 50-100deg.C/s, and maintaining for 3-5min;
5) Annealing the amorphous film subjected to the rapid heating treatment in the step 4) to obtain the lead-free high-entropy ferroelectric film;
the preparation of BNKLST precursor solution in the step 1) is specifically carried out according to the following steps:
weighing bismuth salt, sodium salt, potassium salt, strontium salt, lanthanum salt and titanium salt according to the stoichiometric ratio of the chemical formula;
dissolving the bismuth salt in a solvent, and then adding the sodium salt, the potassium salt, the strontium salt and the lanthanum salt, and dissolving to obtain a solution A;
mixing the titanium salt with a solvent and a chelating agent to obtain a solution B;
adding the solution B into the solution A, adding formamide with the volume ratio of 0.5-1%, stirring for 24-36h, standing for 72-84h, and reacting to obtain BNKLST precursor solution;
the bismuth salt comprises at least one of bismuth acetate, bismuth nitrate and bismuth sulfate; the sodium salt comprises at least one of sodium acetate trihydrate, sodium nitrate and sodium sulfate; the potassium salt comprises at least one of potassium acetate, potassium nitrate and potassium sulfate; the strontium salt comprises at least one of strontium acetate, strontium nitrate and strontium sulfate; the lanthanum salt comprises at least one of lanthanum nitrate hexahydrate, lanthanum nitrate and lanthanum sulfate; the titanium salt is tetrabutyl titanate;
the solvent comprises at least one of glacial acetic acid, ethylene glycol methyl ether, ethanol and isopropanol; the chelating agent comprises at least one of acetylacetone, EDTA, potassium sodium tartrate and ammonium citrate.
2. The method of claim 1, wherein the ratio of x to y is 0.5-2:1.
3. The method according to claim 1, wherein the annealing conditions include: the annealing temperature is 650-700 ℃, and the annealing time is 10-15min.
4. The method of claim 1, wherein steps 2), 3) and 4) are repeated a plurality of times to obtain a multilayer amorphous film before performing step 5).
5. The method according to claim 4, wherein the number of layers of the lead-free high-entropy ferroelectric thin film is 4 to 10, and the thickness of each layer of the lead-free high-entropy ferroelectric thin film is 40 to 50nm.
6. A lead-free high-entropy ferroelectric film, characterized in that it has a breakdown electric field strength of more than 8MV/cm, obtained by the preparation method according to any one of claims 1 to 5.
7. A dielectric energy storage device comprising the lead-free high entropy ferroelectric thin film of claim 6.
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