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CN-121985543-A - Flexible super-compliant electric energy storage film material and preparation method thereof

CN121985543ACN 121985543 ACN121985543 ACN 121985543ACN-121985543-A

Abstract

The invention discloses a flexible supercis electric energy storage thin film material and a preparation method thereof, wherein the flexible supercis electric energy storage thin film material comprises a flexible substrate layer, a buffer layer, a bottom electrode layer and a multiphase solid solution-superlattice layer which are sequentially stacked, the multiphase solid solution-superlattice layer comprises a superlattice layer, the superlattice layer comprises a BaTiO 3 layer and a SrTiO 3 layer which are sequentially and alternately stacked on the bottom electrode layer, a first solid solution and a second solid solution are distributed in the superlattice layer, the first solid solution is BiFeO 3 , the second solid solution is Bi 4‑x Nd x Ti 3 O 12 , and x=0.1-1.5. The flexible super-compliant electric energy storage film material integrates the advantages of a multi-scale structure, has almost hysteresis-free electric hysteresis loops, has excellent energy storage density and energy storage efficiency, and effectively improves the comprehensive energy storage performance of the flexible energy storage film material.

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 flexible supercis electric energy storage thin film material is characterized by comprising a flexible substrate layer, a buffer layer, a bottom electrode layer and a multiphase solid solution-superlattice layer which are sequentially stacked, wherein the multiphase solid solution-superlattice layer comprises a superlattice layer, the superlattice layer comprises a BaTiO 3 layer and a SrTiO 3 layer which are sequentially and alternately stacked on the bottom electrode layer, a first solid solution and a second solid solution are distributed in the superlattice layer, the first solid solution is BiFeO 3 , the second solid solution is Bi 4-x Nd x Ti 3 O 12 , and x=0.1-1.5.
  2. 2. The flexible superclockwise electrical energy storage film material according to claim 1, wherein x=0.6-1.0.
  3. 3. The flexible supercis electric energy storage film material according to claim 1, wherein the flexible substrate layer is one of a PET layer, a PEI layer, a PI layer, a PEN layer, a Mica layer, a PDMS layer, and a metal Ni foil; The buffer layer is one of a SiO 2 layer, a TiO 2 layer, an Al 2 O 3 layer, a SrTiO 3 layer, a CoFe 2 O 4 layer, an Al layer, a YSZ layer and a PMMA layer; The bottom electrode layer is one of a LaNiO 3 layer, a (La, sr) MnO 3 layer, an Au layer, a Pt layer, a SrRuO 3 layer, a TiN layer and an ITO layer; the second solid solution is Bi 3.15 Nd 0.85 Ti 3 O 12 ; The orientation of the flexible substrate layer is one of (001) and (111), the orientation of the buffer layer is one of (001), (011) and (111), the orientation of the bottom electrode layer is one of (001), (011) and (111), and the orientation of the multiphase solid solution-superlattice layer is one of (001), (011) and (111).
  4. 4. The flexible superclockwise electric energy storage film material according to claim 1, wherein the thickness of the buffer layer is 1-20 nm, the thickness of the bottom electrode layer is 20-50 nm, and the thickness of the multiphase solid solution-superlattice layer is 200-300 nm.
  5. 5. The flexible superclockwise electric energy storage film material according to any one of claims 1 to 4, wherein the ratio of thicknesses of the BaTiO 3 layer and the SrTiO 3 layer in the superlattice layer is 1:1 to 10:1.
  6. 6. A method of preparing a flexible superclockwise electrical energy storage film material according to any one of claims 1 to 5 comprising the steps of: s1, providing a flexible substrate layer; s2, depositing a buffer layer on the flexible substrate layer; s3, depositing a bottom electrode layer on the buffer layer; S4, sequentially and alternately depositing a BaTiO 3 layer, a BiFeO 3 layer, a Bi 4-x Nd x Ti 3 O 12 layer and a SrTiO 3 layer on the bottom electrode layer to prepare a multiphase solid solution-superlattice layer rough blank on the bottom electrode layer; And S5, cooling after annealing treatment to obtain the flexible super-compliant electric energy storage film material.
  7. 7. The method for preparing the super-cis electric energy storage film material according to claim 6, wherein in S2-S4, the deposition method 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 in S5, annealing is performed for 10-20min under an oxygen partial pressure atmosphere of 650-800 ℃ and 1-25 mTorr, and then cooling is performed to room temperature at a rate of 6-10 ℃ per min.
  8. 8. The method for preparing the flexible super-cis electric energy storage film material according to claim 6, wherein in S2, a CoFe 2 O 4 target is used as the target, a buffer layer is deposited on a flexible substrate layer through a pulse laser deposition method, the process parameters of the buffer layer deposition are that the vacuum degree of a deposition cavity is 1X 10 -8 ~1×10 -7 Pa, the deposition temperature is 550-650 ℃, the oxygen partial pressure is 30-70 mTorr, the energy of pulse laser is 300-370 mJ, the frequency of the pulse laser is 2-10 Hz, the laser focal length is-20-25 mm, and the deposition number is 1400-2500; S3, using a SrRuO 3 target as a target, and depositing a bottom electrode layer on the buffer layer by a pulse laser deposition method, wherein the process parameters of depositing the bottom electrode layer are that the vacuum degree of a deposition cavity is 1 multiplied by 10 -8 ~1×10 -7 Pa, the deposition temperature is 650-750 ℃, the oxygen partial pressure is 60-100 mTorr, the energy of pulse laser is 320-370 mJ, the frequency of the pulse laser is 2-10 Hz, the laser focal length is 0-35 mm, and the deposition number is 4000-6500; And S4, taking a BaTiO 3 target, a BiFeO 3 target, a Bi 4-x Nd x Ti 3 O 12 target and a SrTiO 3 target as targets, and depositing a multiphase solid solution-superlattice layer rough blank on the bottom electrode layer by a pulse laser deposition method, wherein the process parameters of depositing the multiphase solid solution-superlattice layer rough blank are that the vacuum degree of a deposition cavity is 1 multiplied by 10 -9 ~1×10 -8 Pa, the deposition temperature is 650-800 ℃, the oxygen partial pressure is 1-25 mTorr, the energy of pulse laser is 320-370 mJ, the frequency of the pulse laser is 2-10 Hz, the laser focal length is-45-15 mm, and the total deposition number is 10000-18000.
  9. 9. The method of preparing a flexible superclockwise electrical energy storage film material according to claim 8, wherein S4 comprises the steps of: s4-1, adjusting the distance between the sample table and the target material to be 40-55 cm; Wherein the flexible substrate layer is bonded to the sample stage; S4-2, switching the main target material to the BaTiO 3 target material, setting the deposition number to be 80-350, and setting the rotation speed of the target material to be 5-15 degrees so as to obtain a BaTiO 3 layer by deposition; S4-3, switching the main target material to a BiFeO 3 target material, setting the deposition number to be 15-50, and setting the rotation speed of the target material to be 10-18 degrees so as to obtain a BiFeO 3 layer by deposition; S4-4, switching the main target material to the Bi 4-x Nd x Ti 3 O 12 target material, setting the deposition number to be 5-20, and setting the rotation speed of the target material to be 10-18 degrees so as to obtain a Bi 4-x Nd x Ti 3 O 12 layer by deposition; S4-5, switching the main target material to the SrTiO 3 target material, setting the deposition number to be 15-50, and setting the rotation speed of the target material to be 10-18 degrees so as to obtain a SrTiO 3 layer by deposition; S4-6, repeating the steps S4-2 to S4-5 for 40-60 times to deposit the multiphase solid solution-superlattice layer rough blank on the bottom electrode layer.
  10. 10. The method for preparing the flexible super-compliant electrical energy storage film material according to claim 9, wherein the ratio of the number of deposition in S4-2, the number of deposition in S4-3, the number of deposition in S4-4 and the number of deposition in S4-5 is (10-12): 1-3: (1-3).

Description

Flexible super-compliant electric energy storage film material and preparation method thereof Technical Field The invention relates to a flexible supercis electric energy storage film material and a preparation method thereof, in particular to a multiphase solid solution-superlattice co-modulated flexible supercis electric energy storage film material and a preparation method thereof, and belongs to the technical field of energy storage devices and energy storage. Background The dielectric thin film capacitor has an important application prospect in the next-generation high-performance and high-reliability electronic energy storage system by virtue of excellent stability, adjustable polarization characteristic and quick charge and discharge capability. However, the relatively low storage density of conventional dielectric capacitors has limited its practical application. In recent years, researchers improve the energy storage performance of a dielectric capacitor by regulating the polarization intensity through an atomic/nano scale or increasing the breakdown field intensity through a mesoscale, but these single-scale optimization strategies often cause negative effects on other scales, so that conflicts are generated between the breakdown electric field and the electrical parameters such as the polarization intensity. This inter-scale constraint becomes the bottleneck limiting the overall energy storage performance breakthrough of the dielectric capacitor. The multi-scale engineering strategies such as the composite engineering strategy and the combined engineering strategy can effectively realize the collaborative optimization of a plurality of electrical parameters such as polarization intensity, breakdown electric field and the like by collaborative regulation and control of physical mechanism and structural characteristics under multi-dimension, which is helpful for compensating the limitation that the multi-layer/superlattice interface engineering strategy cannot improve the comprehensive energy storage performance. Compared with other modification methods, the synergistic advantages of solid solution and superlattice interface engineering are particularly outstanding, because the two can simultaneously exert the advantages of interface coupling effect and chemical disorder introduced by the solid solution brought by the superlattice periodic structure by means of the fine structure design of atomic/mesoscale. However, the conventional solid solution strategy is limited by the controllable range of element types and doping concentrations, and in the process of continuously improving the saturation polarization, negative effects such as lattice defect accumulation and leakage current increase caused by excessive doping are difficult to avoid, so that the further improvement of the comprehensive energy storage performance of the film capacitor is restricted. Therefore, how to achieve the synergistic improvement of 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 flexible super-compliant (superparaelectric) energy storage film material with excellent energy storage performance, and the other purpose of the invention is to provide a preparation method of the flexible super-compliant energy storage film material. In order to solve the technical problems, the technical scheme of the invention is as follows: The flexible supercis electric energy storage thin film material comprises a flexible substrate layer, a buffer layer, a bottom electrode layer and a multiphase solid solution-superlattice layer which are sequentially stacked, wherein the multiphase solid solution-superlattice layer comprises a superlattice layer, the superlattice layer comprises a BaTiO 3 layer (barium titanate layer) and a SrTiO 3 layer (strontium titanate layer) which are sequentially and alternately stacked on the bottom electrode layer, a first solid solution and a second solid solution are distributed in the superlattice layer, the first solid solution is BiFeO 3 (bismuth ferrite), and the second solid solution is Bi 4-xNdxTi3O12, and x=0.1-1.5. Further, x=0.11 to 1.2, further, x=0.6 to 1.0, still further, x=0.7 to 0.9. Further, the flexible substrate layer is one of a PET (polyethylene terephthalate) layer, a PEI (polyetherimide) layer, a PI (polyimide) layer, a PEN (polyethylene naphthalate) layer, a Mica (Mica) layer, a PDMS (polydimethylsiloxane) layer and a metal Ni foil; The buffer layer is one of a SiO 2 layer, a TiO 2 layer, an Al 2O3 layer, a SrTiO 3 layer, a CoFe 2O4 layer, an Al layer, a YSZ (yttria stabilized zirconia) layer and a PMMA (polymethyl methacrylate) layer; The bottom electrode layer is one of a LaNiO 3 layer, a (La, sr) MnO 3 layer, an Au layer, a Pt layer, a SrRuO 3 layer, a TiN layer a