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CN-121985542-A - Super-compliant electric energy storage film material and preparation method thereof

CN121985542ACN 121985542 ACN121985542 ACN 121985542ACN-121985542-A

Abstract

The invention discloses a supercis electric energy storage thin film material and a preparation method thereof, wherein the supercis electric energy storage thin film material comprises a substrate layer, a bottom electrode layer and a superlattice-solid solution dielectric layer which are sequentially stacked, the superlattice-solid solution dielectric layer comprises a superlattice layer, the superlattice layer is formed by sequentially and alternately stacking a BaTiO 3 layer and a SrTiO 3 layer, solid solutions are distributed in the superlattice layer, and the solid solutions are BiFeO 3 . The super-compliant electric energy storage film material integrates the advantages of a multi-scale structure, has a longer electric hysteresis loop, and has excellent energy storage density and energy storage efficiency.

Inventors

  • ZHONG GAOKUO
  • CHEN JIANXIN
  • Dai Liyufen

Assignees

  • 湖南大学
  • 岳麓山工业创新中心

Dates

Publication Date
20260505
Application Date
20260407

Claims (10)

  1. 1. The super-cis electric energy storage thin film material is characterized by comprising a substrate layer, a bottom electrode layer and a superlattice-solid solution dielectric layer which are sequentially stacked, wherein the superlattice-solid solution dielectric layer comprises a superlattice layer, the superlattice layer is formed by sequentially and alternately stacking a BaTiO 3 layer and a SrTiO 3 layer, solid solution is distributed in the superlattice layer, and the solid solution is BiFeO 3 .
  2. 2. The super-compliant electrically energy storage thin film material of claim 1, wherein the substrate layer is one of LaAlO 3 layer, srTiO 3 layer, dyScO 3 layer, tbScO 3 layer, mgO layer, si layer, YSZ layer and Al 2 O 3 layer, and the bottom electrode layer is one of LaNiO 3 layer, (La, sr) MnO 3 layer, srRuO 3 layer, tiN layer and ITO layer.
  3. 3. The supercis electrical energy storage thin film material of claim 1, wherein the substrate layer is oriented (111), the bottom electrode layer is oriented one of (001), (011) and (111), and the superlattice-solid solution dielectric layer is oriented one of (001), (011) and (111).
  4. 4. The super-compliant electrically energy storage thin film material of claim 1, wherein the thickness of the bottom electrode layer is 5-35 nm and the thickness of the superlattice-solid solution dielectric layer is 400-550 nm.
  5. 5. The super-compliant electrical energy storage thin film material as claimed in any of claims 1-4, wherein the ratio of the thicknesses of BaTiO 3 layer and SrTiO 3 layer in the superlattice layer is 2:1-20:1.
  6. 6. A method of preparing a superclockwise electric energy storage film material as claimed in any one of claims 1 to 5 comprising the steps of: s1, providing a substrate layer; S2, depositing a bottom electrode layer on the substrate layer; S3, sequentially and alternately depositing a BaTiO 3 layer, a SrTiO 3 layer and a BiFeO 3 layer on the bottom electrode layer to prepare a superlattice-solid solution dielectric layer rough blank on the bottom electrode layer; And S4, cooling after annealing treatment to obtain the super-compliant electric energy storage film material.
  7. 7. The method for preparing a super-clockwise electric energy-storage thin film material according to claim 6, wherein the deposition method in S2-S3 is one of an electrochemical method, a pulse laser deposition method, a high-flux pulse laser deposition method, a magnetron sputtering method and an atomic layer deposition method, and/or the method comprises the steps of annealing at 500-750 ℃ for 5-15min in an oxygen partial pressure atmosphere of 1-20 mTorr in S4, and cooling to room temperature.
  8. 8. The method for preparing the super-cis electric energy storage film material according to claim 6, wherein in S2, srRuO 3 target is used as target, a bottom electrode layer is deposited on a substrate layer through a pulse laser deposition method, the process parameters of the deposited bottom electrode layer are that the vacuum degree of a deposition cavity is 1X 10 -8 ~1×10 -6 Pa, the deposition temperature is 550-700 ℃, the oxygen partial pressure is 90-150 mTorr, the energy of pulse laser is 270-370 mJ, the frequency of the pulse laser is 1-10 Hz, the laser focal length is-30 mm, and the deposition number is 1000-3500; And S3, preparing a superlattice-solid solution dielectric layer rough blank on the bottom electrode layer by using a BaTiO 3 target, a SrTiO 3 target and a BiFeO 3 target as targets through a pulse laser deposition method, wherein the process parameters of preparing the superlattice-solid solution dielectric layer rough blank are that the vacuum degree of a deposition cavity is 1 multiplied by 10 -8 ~1×10 -6 Pa, the deposition temperature is 500-700 ℃, the oxygen partial pressure is 1-20 mTorr, the energy of pulse laser is 270-335 mMJ, the frequency of the pulse laser is 1-10 Hz, the laser focal length is 0-50 mm, and the total deposition number is 10000-20000.
  9. 9. The method for preparing a superclockwise electric energy storage film material according to claim 8, wherein the step S3 comprises the following steps: s3-1, adjusting the distance between the sample stage and the target material to be 40-65 cm; wherein the substrate layer is adhered to the sample stage; S3-2, switching the main target material to the BaTiO 3 target material, setting the deposition number to be 100-300, and setting the rotation speed of the target material to be 5-20 degrees so as to obtain a BaTiO 3 layer by deposition; S3-3, switching the main target material to the SrTiO 3 target material, setting the deposition number to be 10-50, and setting the rotation speed of the target material to be 10-20 degrees so as to obtain a SrTiO 3 layer by deposition; S3-4, switching the main target material to a BiFeO 3 target material, setting the deposition number to be 5-25, and setting the rotation speed of the target material to be 10-20 degrees so as to obtain a BiFeO 3 layer by deposition; S3-5, repeating the steps S3-2-S3-4 for 40-200 times to deposit the superlattice-solid solution dielectric layer rough blank on the bottom electrode layer.
  10. 10. The method for preparing a super-compliant electrically-deposited thin film material as claimed in claim 9, wherein the ratio of the number of deposition in S3-4 to the total number of deposition in S3 is 1:13-30; and/or the ratio of the deposition number in S3-2, the deposition number in S3-3 and the deposition number in S3-4 is 10-24:1.5-5:1.

Description

Super-compliant electric energy storage film material and preparation method thereof Technical Field The invention relates to a supercis electric energy storage film material and a preparation method thereof, in particular to a supercis electric energy storage film material with a superlattice-solid solution multi-scale structure and a preparation method thereof, belonging to the technical field of energy storage devices and energy storage. Background The high-performance energy storage film has important application potential due to the rapid charge and discharge capability and high power density. For energy storage films, energy storage density and energy storage efficiency are key indicators for evaluating the energy storage performance of the energy storage film, reflecting storable energy per unit volume, wherein improving the breakdown electric field and maximizing the polarization intensity difference are effective strategies for achieving excellent capacitor performance. Among various capacitor energy storage medium film materials, ferroelectric materials are one of the most promising candidate materials for high-performance capacitors due to high breakdown strength, large saturated polarization and excellent fatigue resistance. Hysteresis switching of large ferroelectric domains results in large remnant polarization and low energy storage efficiency, which presents a significant challenge for improving the energy storage properties of ferroelectric materials. The independent engineering strategy can effectively improve the breakdown strength or maximize the polarization strength difference, thereby improving the energy storage performance. However, such a boost typically results in unilateral optimization of energy storage density or energy storage efficiency, failing to achieve an optimal balance between the two, fundamentally limiting the possibilities of simultaneously boosting energy storage density and energy storage efficiency, which presents a greater challenge for improving the overall energy storage performance of the energy storage film. The Chinese patent application CN116121704A discloses a high-flux thickness gradient film which comprises a basal layer, a bottom electrode layer and a functional layer, wherein the basal layer and the functional layer are sequentially grown on the basal layer, the functional layer is made of a BaTiO 3 film, the basal layer is one of a SrTiO 3 substrate, a GdSiO 3 substrate, a DyScO 3 substrate and a mica substrate, the SrTiO 3 substrate is one of (110), (111) and (100), and the bottom electrode layer is one of a SrRuO 3 film and a La 0.67Sr0.33MnO3 film. But this patent application does not consider how to increase the energy storage density or energy storage efficiency of the high flux thickness gradient film. The Chinese patent CN110452421B discloses a dielectric composite material based on core-shell structure filler, which comprises a ceramic material and a polymer, wherein the ceramic material is in a core-shell structure, the dielectric constant of the shell structure is smaller than that of the core structure, the material of the shell structure and the material of the core structure are both in a perovskite structure, the core structure material is BaTiO 3 in the core-shell structure, the shell structure material is SrTiO 3, and the SrTiO 3 is epitaxially grown on the surface of BaTiO 3. The dielectric composite material is difficult to realize the synergistic improvement of the discharge energy density and the energy storage efficiency, the discharge energy density can only reach 13.89J/cm 3, and the energy storage efficiency at the moment is lower than 55%. Therefore, how to synchronously improve the energy storage density and the energy storage efficiency of the energy storage thin film material is a problem to be solved by those skilled in the art. Disclosure of Invention Aiming at the defects of the prior art, one of the purposes of the invention is to provide a super-cis electric (superparaelectric) energy storage film material with excellent energy storage density and energy storage efficiency, and the other purpose of the invention is to provide a preparation method of the super-cis electric energy storage film material. In order to solve the technical problems, the technical scheme of the invention is as follows: The super-cis electric energy storage thin film material comprises a substrate layer, a bottom electrode layer and a superlattice-solid solution dielectric layer which are stacked in sequence, wherein the superlattice-solid solution dielectric layer comprises a superlattice layer, the superlattice layer is formed by alternately stacking a BaTiO 3 layer (barium titanate layer) and a SrTiO 3 layer (strontium titanate layer) in sequence, solid solutions are distributed in the superlattice layer, and the solid solutions are BiFeO 3 (bismuth ferrite). Further, the substrate layer is one of LaAlO 3 layer, srTiO 3 layer, dyScO 3 layer,