CN110767473B - Flexible energy storage film - Google Patents

Flexible energy storage film Download PDF

Info

Publication number
CN110767473B
CN110767473B CN201811196365.0A CN201811196365A CN110767473B CN 110767473 B CN110767473 B CN 110767473B CN 201811196365 A CN201811196365 A CN 201811196365A CN 110767473 B CN110767473 B CN 110767473B
Authority
CN
China
Prior art keywords
film
energy storage
flexible
metal
strontium titanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811196365.0A
Other languages
Chinese (zh)
Other versions
CN110767473A (en
Inventor
冯雪
王志建
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Institute of Flexible Electronics Technology of THU Zhejiang
Original Assignee
Tsinghua University
Institute of Flexible Electronics Technology of THU Zhejiang
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsinghua University, Institute of Flexible Electronics Technology of THU Zhejiang filed Critical Tsinghua University
Priority to CN201811196365.0A priority Critical patent/CN110767473B/en
Publication of CN110767473A publication Critical patent/CN110767473A/en
Application granted granted Critical
Publication of CN110767473B publication Critical patent/CN110767473B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/088—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or Pb and B representing a refractory or rare earth metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/33—Thin- or thick-film capacitors 
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

The invention relates to a flexible energy storage film. The flexible energy storage film comprises a flexible metal substrate, and a metal film and a strontium titanate layer which are sequentially formed on the flexible metal substrate; the surface of the strontium titanate layer, which is attached to the metal film, is a diffusion solid solution layer which is doped by diffusing metal atoms in the metal film to the strontium titanate layer. The energy storage film disclosed by the invention not only realizes flexibility, but also has higher breakdown field strength, energy storage density and binding force. After multiple times of bending, the retention rate of the energy storage density and the stability of the binding force are good, and the reliability of the flexible energy storage film is high.

Description

Flexible energy storage film
The application is that the application number is: 201810829730.0, having application date of 7 and 25 in 2018 and the name of: the invention discloses a flexible energy storage film, a preparation method thereof and a divisional application of the invention application of a film capacitor.
Technical Field
The invention relates to the field of energy sources, in particular to a flexible energy storage film.
Background
With the gradual trend toward miniaturization, multi-functionality, and light weight of electronic devices, electronic components constituting the electronic devices also need to be developed toward miniaturization, light weight, high integration, and multi-functionality.
For a thin film capacitor, a desirable approach to achieve miniaturization is to increase the capacitance by increasing the dielectric constant of the dielectric thin film. The dielectric film mainly comprises a high-molecular energy storage film and a ceramic energy storage film, and in the traditional film capacitor, the used dielectric film is mainly the high-molecular energy storage film. Because the dielectric constant of the ceramic energy storage film is far higher than that of the polymer energy storage film, the ceramic energy storage film is used for replacing the polymer energy storage film, and the development trend of the film capacitor is met. However, ceramic energy storage films lack the flexibility of polymeric energy storage films.
Disclosure of Invention
Based on this, it is necessary to provide a flexible energy storage film aiming at the problem of insufficient flexibility of the ceramic energy storage film; the preparation method realizes the flexibility of the energy storage film, simultaneously enables the energy storage film to have high reliability and high energy storage density, and can be used as a dielectric material of a film capacitor.
A flexible energy storage thin film comprises a flexible metal substrate, and a metal thin film and a strontium titanate layer which are sequentially formed on the flexible metal substrate;
the surface of the strontium titanate layer, which is attached to the metal film, is a diffusion solid solution layer which is doped by diffusing metal atoms in the metal film to the strontium titanate layer.
In one embodiment, the thickness of the metal thin film is 5nm to 95 nm.
In one embodiment, the metal film is one of a strontium film, a calcium film, a barium film and a lead film.
In one embodiment, the thickness of the strontium titanate layer is 10nm to 2 μm, and the grain size is 30nm to 500 nm.
In one embodiment, the thickness of the diffusion solid solution layer is 5 nm-10 nm, the grain size is 20 nm-300 nm, and the metal atom in the diffusion solid solution layer is one of strontium, calcium, barium and lead.
In one embodiment, the thickness of the flexible metal substrate is 12-18 μm.
In one embodiment, the surface roughness of the flexible metal substrate is 0.4 μm to 0.8 μm.
In one embodiment, the flexible metal substrate has a surface tension ≧ 60 dynes.
In one embodiment, the flexible metal substrate comprises one of copper foil, titanium foil, silver foil, gold foil, platinum foil, aluminum foil, nickel foil, chromium foil, and tin foil.
In one embodiment, the minimum bending radius of the flexible energy storage film is 2-15 mm; and/or
The breakdown field strength of the flexible energy storage film is 1000 kV/cm-3000 kV/cm; and/or
The energy storage density of the flexible energy storage film is 12J/cm3～55J/cm3(ii) a And/or
The adhesive force between the metal film and the flexible metal substrate is 5B; and/or
And the adhesion force between the diffusion solid solution layer and the metal film is 5B.
The energy storage film disclosed by the invention not only realizes flexibility, but also has higher breakdown field strength, energy storage density and binding force. After multiple times of bending, the retention rate of the energy storage density and the stability of the binding force are good, and the reliability of the flexible energy storage film is high.
Drawings
FIG. 1 is a schematic structural diagram of a flexible energy storage film according to the present invention, in which a is a schematic structural diagram of the flexible energy storage film before heat treatment, and b is a schematic structural diagram of the flexible energy storage film after heat treatment;
FIG. 2 is a schematic diagram of the magnetic filtering multi-arc ion plating method of the present invention.
In the figure: 1. a vacuum arc source; 2. a lighting device; 3. a visible window; 4. filtering the magnetic field; 5. a focusing magnetic field; 6. a vacuum chamber; 10. a flexible metal substrate; 11. a target material; 12. electrons; 13. a metal droplet; 14. ions; 15. a metal atom; 20. a metal thin film; 30. a strontium titanate pre-fabricated layer; 31. a ceramic film; 311. a diffusion solid solution layer; 312. a strontium titanate layer.
Detailed Description
The flexible energy storage film provided by the invention will be further explained with reference to the attached drawings.
As shown in fig. 1, the preparation method of the flexible energy storage thin film provided by the invention comprises the following steps:
(a) providing a flexible metal substrate 10;
(b) depositing a metal film 20 on the flexible metal substrate 10 by using a magnetic filtration multi-arc ion plating method by taking a metal simple substance as a target material;
(c) depositing a strontium titanate prefabricated layer 30 on the metal film 20 by a magnetron sputtering method by taking strontium titanate as a target material;
(d) the flexible metal substrate 10 deposited with the metal thin film 20 and the strontium titanate prefabricated layer 30 is subjected to heat treatment, so that metal atoms in the metal thin film 20 are diffused to the strontium titanate prefabricated layer 30, and a ceramic thin film 31 is obtained, wherein the ceramic thin film 31 comprises a diffusion solid solution layer 311 and a strontium titanate layer 312, which are sequentially attached to the metal thin film 20 and are doped with strontium titanate.
In step (a), the material of the flexible metal substrate 10 is not limited as long as it has good flexibility, strong high-temperature oxidation resistance, conductivity and no reaction with the ceramic film, and includes one of copper foil, titanium foil, silver foil, gold foil, platinum foil, aluminum foil, nickel foil, chromium foil and tin foil, and may also be one of copper alloy, titanium alloy, silver alloy, gold alloy, platinum alloy, aluminum alloy, nickel alloy, chromium alloy and tin alloy.
Considering that copper foil is the most cost-effective metal material in the field of electronic industry, its resistivity is 1.75X 10-8Omega. m, second only to silver (1.65X 10)-8Ω · m), a thermal conductivity 401W/(m · K), next to silver (420W/(m · K)), while the price of copper is much lower than that of silver. Secondly, industrial copper foil is mature, the copper foil is divided into rolled copper foil and electrolytic copper foil, and the rolled copper foil and the electrolytic copper foil are subjected to electroplating treatment to prevent oxidation and high-temperature oxidation, and cannot be oxidized when being calcined in air. Therefore, the flexible metal substrate 10 is preferably a copper foil.
Further, the rolled copper foil is composed of rod-shaped grains parallel to the surface of the copper foil and has superior bending resistance, and the electrolytic copper foil is composed of rod-shaped grains perpendicular to the surface of the copper foil and has lower bending resistance than the rolled copper foil, and therefore, the copper foil is preferably a rolled copper foil.
The thinner the flexible metal substrate 10 is, the better the flexibility is, and therefore, the thickness of the flexible metal substrate 10 is 12 to 18 μm, and more preferably, a rolled copper foil of 12 μm.
In the film capacitor, the flexible metal substrate 10 is used as an electrode, the actual contact area of the metal film 20 with the electrode is related to the surface roughness of the flexible metal substrate 10, and the larger the surface roughness is, the larger the actual contact area is, and the larger the capacitance value per geometric area is. However, the surface roughness of the flexible metal substrate 10 is too large, which easily causes holes on the surface of the metal film 20, and affects the energy storage performance of the flexible energy storage film. Therefore, the surface roughness of the flexible metal substrate 10 is 0.4 μm to 0.8 μm.
The surface tension of the flexible metal substrate 10 is greater than or equal to 60 dynes, preferably, the surface tension of the flexible metal substrate 10 is greater than 60 dynes, and the higher the surface tension of the flexible metal substrate 10 is, the stronger the bonding force between the metal film 20 and the flexible metal substrate 10 is.
The surface activity can be increased by treating the surface of the flexible metal substrate 10, thereby increasing the surface tension. Preferably, the treatment method comprises the following steps: firstly heating a flexible metal substrate 10, setting the temperature to be 100-300 ℃, preserving the heat for 10-30 minutes, and then processing the flexible metal substrate by adopting a Hall ion source, wherein the voltage of the Hall ion source is 800-2000V, the current is 0.5-2A, and the processing time is 1-10 min.
In the step (b), the metal film 20 is used as a transition layer, and the metal film 20 can be prepared by a sol-gel method, a magnetron sputtering method, a pulsed laser sputtering deposition method, a hydrothermal method, and the like, but the metal film 20 prepared by these methods has low energy of particle deposition, and the bonding force between the metal film 20 and the flexible metal substrate 10 is poor, so that the reliability of the flexible energy storage film is low. Therefore, the invention adopts a magnetic filtration multi-arc ion plating method to deposit and form the metal film 20 on the flexible metal substrate 10.
As shown in FIG. 2, the magnetic filtering multi-arc ion plating device of the invention comprises a vacuum arc source 1, a lighting device 2, a visible window 3, a filtering magnetic field 4 and a focusing magnetic field 5, wherein a flexible metal substrate 10 is positioned in a vacuum cavity 6. The magnetic filtration multi-arc ion plating method comprises the steps that electric arcs generated by arcing are combusted on the surface of a metal simple substance target 11, the metal simple substance target 11 is liquefied to generate ions 14, electrons 12 and metal liquid drops 13, particles (the ions 14 and the electrons 12) with charges are accelerated by an electric field and pass through a filtration magnetic field, the charged particles move along magnetic lines of force, and the uncharged metal liquid drops 13 are filtered by the filtration magnetic field. After filtering, the pure particles enter the vacuum chamber 6 through the focusing magnetic field 5, and are deposited on the flexible metal substrate 10 by the bias electric field applied to the flexible metal substrate 10. In the whole process, the electrons 12 are gathered and accelerated to form a moving electron cloud, the electron cloud and the ions 14 form a strong electric potential after being separated, the ions 14 are extracted and deposited on the flexible metal substrate 10 together with the electrons 12, the magnetic filtration multi-arc ion plating process is completed, and the metal film 20 is formed.
In the magnetic filtration multi-arc ion plating process, accelerated electrons 12 continuously impact the surface of the flexible metal substrate 10 to clean and activate the surface of the flexible metal substrate 10, so that the surface activity of the flexible metal substrate 10 is enhanced, and the bonding force with the deposited metal film 20 is strong. Furthermore, the energy of the particles can be controlled by adjusting the extraction electric field and the bias voltage. Therefore, the particle energy of the metal film 20 formed by the magnetic filtration multi-arc ion plating method is higher by one order of magnitude than the particle energy of the metal film 20 formed by the magnetron sputtering method and the like, and further, the metal film 20 formed by the magnetic filtration multi-arc ion plating method has higher bonding force with the flexible metal substrate 10, and the reliability of the flexible energy storage film is high.
Preferably, the working atmosphere of the magnetic filtration multi-arc ion plating method is argon, and Ar is generated after argon ionization+The target material is impacted under the action of the electric field. The introducing flow of the argon is 10 sccm-30 sccmm, vacuum degree of 2.0X 10-2Pa～4.0×10-2Pa. Ar in the chamber+The more kinetic energy is generated, the more favorable the target ions escape.
Preferably, the arc current of the magnetic filtration multi-arc ion plating method is 45A-60A, the extraction current is 7A-11A, the bias voltage applied to the flexible metal substrate is 5V-10V, and the deposition time is 30 seconds-180 seconds.
Further, the thickness of the deposited metal film 20 is 10nm to 100 nm.
Preferably, the metal is preferably one of strontium, calcium, barium and lead.
In the step (c), a strontium titanate prefabricated layer 30 is deposited on the metal film 20 by using a magnetron sputtering process. Under the action of the electric field and the magnetic field, ions in high-speed spiral motion bombard the strontium titanate target material, and atoms or ion groups bombarded from the strontium titanate target material are deposited on the metal film 20 to form a strontium titanate prefabricated layer 30. Because the magnetron sputtering particles have energy as high as 1eV to 10eV, and the surface mobility of the metal film 20 can be maintained high, the formed strontium titanate prefabricated layer 30 has good crystallization performance and high deposition efficiency, the temperature required for forming the strontium titanate prefabricated layer 30 is low, and the compatibility with an integration process is good.
Compared with PLD, sol-gel, hydrothermal method and the like, the method for forming the strontium titanate prefabricated layer 30 on the metal film 20 by deposition through the magnetron sputtering process has the advantages of high deposition efficiency, good film forming crystallinity and the like, and is beneficial to improving the energy storage performance of the flexible energy storage film. And the whole process is a physical process, and oxygen cooling protection is not needed when film forming is finished, so that the flexible metal substrate 10 and the metal film 20 are protected from being oxidized.
If the compactness of the strontium titanate target is not high, the surface and internal air holes of the strontium titanate target are more, and the strontium titanate target is easy to generate microcracks under the action of high pressure and high temperature during magnetron sputtering, and the microcracks expand to cause the strontium titanate target to crack. Therefore, the compactness of the strontium titanate target is preferably equal to or more than 96 percent, and more preferably more than 96 percent, so that the target is convenient for magnetron sputtering and works stably.
In the magnetron sputtering process, the working atmosphere of the magnetron sputtering method is argon, the flow of the argon is 30 sccm-120 sccm, and the vacuum degree is 0.1 Pa-0.5 Pa. In the magnetron sputtering method, the magnetron sputtering power is 50W-200W, and the deposition time is 1 min-60 min.
Furthermore, the thickness of the strontium titanate prefabricated layer 30 obtained by deposition is 30 nm-3 μm, the grain size is 10 nm-450 nm, and the film structure is compact.
In the step (d), the flexible metal substrate 10 on which the metal thin film 20 and the strontium titanate preform layer 30 are deposited is heat-treated. In the heat treatment process, when the metal thin film 20 is a strontium thin film, strontium atoms are diffused into the strontium titanate pre-layer 30 during the heat treatment process, and the strontium atoms are doped to form a non-stoichiometric strontium titanate diffusion solid solution layer 311. In the nonstoichiometric strontium titanate, excessive strontium atoms are difficult to enter crystal lattices to generate titanium vacancies, so the strontium atoms exist in crystal boundaries to play a pinning role and inhibit the growth of crystal grains, thereby being favorable for reducing the crystal grain size of the diffusion solid solution layer 311 and improving the breakdown field strength and the energy storage density. Similarly, titanates of calcium, barium and lead have the same structure as strontium titanate and can partially replace strontium. Accordingly, when the metal thin film 20 is a calcium thin film, a barium thin film, or a lead thin film, accordingly, calcium atoms, barium atoms, or lead atoms are diffused into the strontium titanate preform layer 30 during the heat treatment to form a calcium atom-doped strontium titanate diffusion solid solution layer 311, or a barium ion-doped strontium titanate diffusion solid solution layer 311, or a lead ion-doped strontium titanate diffusion solid solution layer 311.
Meanwhile, in the heat treatment process, Sr, Ti, and O atoms in the strontium titanate preform layer 30 may exchange energy with each other depending on lattice vibration, and some atoms at distorted positions may be restored to a normal state. Alternatively, the Sr, Ti, and O atoms have increased mobility, and some of the vacancies, interstitial atoms, and dislocations that were "frozen" will recombine within the film, or migrate to the surface and grain boundaries and disappear, or combine into a lower energy defect configuration (e.g., dislocation loops, vacancy clusters, etc.). Therefore, the heat treatment can largely eliminate the lattice mismatch, lattice reconstruction, impurities, phase transition, and other non-equilibrium defects in the strontium titanate preform layer 30, thereby obtaining the strontium titanate layer 312. The diffusion solid solution layer 311 and the strontium titanate layer 312 together form the ceramic thin film 31, and compared with the strontium titanate prefabricated layer 30, the internal stress of the ceramic thin film 31 is significantly reduced, and the bonding force between the ceramic thin film 31 and the metal thin film 20 is higher.
The ceramic thin film 31 is composed of a diffusion solid solution layer 311 and a strontium titanate layer 312, and the thickness of the diffusion solid solution layer 311 is controlled by the temperature and time of the heat treatment, i.e., the thickness of the diffusion solid solution layer 311 is increased, and the thickness of the strontium titanate layer is correspondingly decreased. Preferably, the temperature of the heat treatment is 300-500 ℃ and the time is 30-300 minutes. The thickness of the obtained diffusion solid solution layer 311 is 5 nm-10 nm, the thickness of the strontium titanate layer 312 is 10 nm-2 μm, and the ceramic thin film 31 has higher energy storage performance while the bonding force between the ceramic thin film 31 and the metal thin film 20 is ensured.
Preferably, argon gas is introduced during the heat treatment, the flow rate of the argon gas is 100sccm to 200sccm, and the vacuum degree is 0.1Pa to 1 Pa. The metal atoms in the metal thin film 20 have high activity, and the metal thin film can be prevented from being oxidized by performing heat treatment in an argon atmosphere.
According to the invention, the flexible energy storage film is formed by depositing the flexible metal substrate on the flexible metal substrate sequentially through a magnetic filtration multi-arc ion plating method to form a metal film and depositing the ceramic film on the metal film through a magnetron sputtering process, so that the flexibility of the ceramic energy storage film is realized, the magnetic filtration multi-arc ion plating method and the magnetron sputtering method are carried out in the same chamber, the preparation efficiency is high, the microstructure of the ceramic film, such as the crystallinity and the grain size, is good, the internal stress is low, and the energy storage performance of the flexible energy storage film is improved.
Meanwhile, the metal film obtained by deposition through a magnetic filtration multi-arc ion plating method has high particle energy, and the metal film has strong binding force with the flexible metal substrate. And after heat treatment, metal atoms of the metal film can diffuse to the strontium titanate prefabricated layer, on one hand, a diffusion solid solution layer and a strontium titanate layer of the metal atom doped with strontium titanate are formed, the bonding force between the ceramic film and the metal film is improved, on the other hand, the metal atoms can play a pinning role at a strontium titanate crystal boundary, the growth of crystal grains is inhibited, the diffusion solid solution layer has smaller crystal grains, and the energy storage performance of the ceramic film is improved. Therefore, the flexible energy storage film has good energy storage density retention rate and good binding force stability after being bent for many times, and further has high reliability.
As shown in fig. 1 b, the present invention further provides a flexible energy storage thin film, which includes a flexible metal substrate 10, and a metal thin film 20 and a ceramic thin film 31 sequentially formed on the flexible metal substrate 10, wherein the ceramic thin film 31 includes a diffusion solid solution layer 311 and a strontium titanate layer 312, which are sequentially attached to the metal thin film 20 and are doped with strontium titanate by metal atoms.
Preferably, the flexible energy storage film is prepared by the preparation method.
The thickness of the strontium titanate layer 312 is 10 nm-2 μm, and the grain size is 30 nm-500 nm.
The thickness of the metal film 20 is 5 nm-95 nm, and the metal film is one of a strontium film, a calcium film, a barium film and a lead film.
The thickness of the diffusion solid solution layer 311 is 5nm to 10nm, and the metal atom in the diffusion solid solution layer 311 is one of strontium, calcium, barium and lead.
The thickness of the flexible metal substrate 10 is 12-18 μm; and/or
The surface roughness of the flexible metal substrate 10 is 0.4-0.8 μm; and/or
The surface tension of the flexible metal substrate 10 is not less than 60 dynes; and/or
The flexible metal substrate 10 includes one of a copper foil, a titanium foil, a silver foil, a gold foil, a platinum foil, an aluminum foil, a nickel foil, a chromium foil, and a tin foil.
The minimum bending radius of the flexible energy storage film is 2-15 mm; and/or
The breakdown field strength of the flexible energy storage film is 1000 kV/cm-3000 kV/cm; and/or
The energy storage density of the flexible energy storage film is 12J/cm3～55J/cm3(ii) a And/or
The adhesive force between the metal film and the flexible metal substrate is 5B; and/or
The adhesive force between the ceramic film and the metal film is 5B.
The energy storage film disclosed by the invention not only realizes flexibility, but also has higher breakdown field strength, energy storage density and binding force. After multiple times of bending, the retention rate of the energy storage density and the stability of the binding force are good, and the reliability of the flexible energy storage film is high.
The invention also provides a film capacitor, which comprises the flexible energy storage film.
The flexible energy storage film provided by the invention is used for replacing a high polymer film, and the development of a film capacitor towards the trends of miniaturization, lightness, thinness, high integration and multiple functions can be promoted. Meanwhile, the film capacitor has the advantages of no polarity, high insulation resistance, excellent frequency characteristics (wide frequency response), small dielectric loss and the like. The method can be applied to a plurality of industries such as electronics, household appliances, communication, electric power, electrified railways, new energy vehicles, wind power generation, solar power generation and the like. Especially in the signal cross connection part, the thin film capacitor with good frequency characteristic and low dielectric loss of the invention can ensure that the signal is not distorted too much when being transmitted, and has good electrical performance and high reliability.
Hereinafter, the flexible energy storage film will be further described by the following specific examples.
Example 1:
using flexible rolled copper foil as substrate, the thickness is 18 micrometers, surface roughness is 0.4 micrometers, placing in vacuum chamber, vacuum-pumping to 3X 10-3Pa. Heating the vacuum chamber to 150 ℃, keeping the temperature for 10min, introducing argon gas, controlling the argon gas flow to be 30sccm, opening the Hall ion source, setting the voltage of the Hall ion source to be 1000v and the current to be 0.5A, and treating for 1min to enable the surface tension of the copper foil to reach 60 dynes.
Closing the gate valve to a vacuum degree of 2.0X 10-2Pa, keeping the flow of argon gas at 30sccm, turning on a magnetic filtration multi-arc ion plating power supply, adjusting the arc current to 50A, leading out current 9A, and applying to the flexible rolled copper foilThe upper bias voltage is 5V, a strontium target is used as a metal simple substance target material, the deposition time is 30s, and a 10nm strontium film is formed on the copper foil.
Turning off a magnetic filtration multi-arc ion plating power supply, turning on a large argon flow to 100sccm, enabling the vacuum degree of a vacuum chamber to be 0.4Pa, turning on a magnetron sputtering power supply to 80W, taking strontium titanate with the density of 96% as a target material, depositing for 1min, forming a 30nm strontium titanate prefabricated layer on the metal film, wherein the grain size of the strontium titanate prefabricated layer is 10nm, the structure is compact, and the structure of the flexible energy storage film is shown as a in figure 1.
And (2) closing the magnetron sputtering power supply, opening the heating power supply, setting the argon flow to be 100sccm, the vacuum degree to be 0.1Pa, the heating temperature to be 300 ℃, keeping the temperature for 30min, and diffusing strontium atoms in the strontium thin film to the strontium titanate prefabricated layer to obtain the ceramic thin film, wherein the ceramic thin film comprises a diffusion solid solution layer and a strontium titanate layer which are sequentially attached to the strontium thin film and have non-stoichiometric ratio, and the specific structure is shown as b in figure 1.
Copper metal is deposited on the strontium titanate layer of the flexible energy storage film shown in the b in the figure 1 through a magnetron sputtering process to be used as an upper electrode, and an electrical property test is carried out.
Tests prove that the thickness of a strontium film in the obtained flexible energy storage film is 5nm, the thickness of a diffusion solid solution layer is 5nm, the grain size of the diffusion solid solution layer is 20nm, the thickness of a strontium titanate layer is 10nm, the grain size of the strontium titanate layer is 30nm, the bonding force of the strontium film and a copper foil is 5B, the bonding force of the strontium film and a ceramic film is 5B, the minimum bending radius of the flexible energy storage film is 4mm, the breakdown field strength is 1800kV/cm, and the energy storage density is 30J/cm3After 1000 times of bending, the bonding force between layers is 5B, and the energy storage density is 30J/cm3The retention rate is 100%, and the method can be applied to film capacitors.
Example 2:
using flexible silver foil as substrate, thickness of 12 micrometers and surface roughness of 0.5 micrometers, placing in vacuum chamber, vacuumizing to 3X 10-3Pa. Heating the vacuum chamber to 200 deg.C, maintaining for 10min, introducing argon gas with flow of 30sccm, opening Hall ion source, and setting Hall ionThe voltage of the sub-source is 1000v, the current is 0.5A, and the treatment is carried out for 5min, so that the surface tension of the silver foil reaches 70 dynes.
Closing the gate valve to a vacuum degree of 2.0X 10-2Pa, keeping the flow of argon gas at 30sccm, turning on a magnetic filtration multi-arc ion plating power supply, adjusting the arc current to 55A, leading out a current of 9A, applying a bias voltage of 10V on the flexible silver foil, taking a calcium target as a metal simple substance target material, depositing for 60s, and forming a 40nm calcium film on the copper foil.
And (2) closing a magnetic filtration multi-arc ion plating power supply, opening the flow of large argon to 100sccm to ensure that the vacuum degree of a vacuum chamber is 0.4Pa, opening a magnetron sputtering power supply to 100W, taking strontium titanate with the density of 97% as a target material, depositing for 2min to form a 60nm strontium titanate prefabricated layer on the metal film, wherein the grain size of the strontium titanate prefabricated layer is 15nm, the structure is compact, and the structure of the flexible energy storage film is shown as a in figure 1.
And (2) closing the magnetron sputtering power supply, opening the heating power supply, setting the argon flow to be 120sccm, the vacuum degree to be 0.3Pa, the heating temperature to be 350 ℃, keeping the temperature for 30min, and diffusing calcium atoms in the calcium thin film to the strontium titanate prefabricated layer to obtain a ceramic thin film, wherein the ceramic thin film comprises a calcium-doped strontium titanate diffusion solid solution layer and a strontium titanate layer which are sequentially attached to the calcium thin film, and the specific structure is shown as b in figure 1.
And (3) depositing gold metal on the strontium titanate layer of the flexible energy storage film shown in the b in the figure 1 as an upper electrode through a magnetron sputtering process, and performing an electrical property test.
Tests prove that the thickness of a calcium film in the obtained flexible energy storage film is 30nm, the thickness of a diffusion solid solution layer is 7nm, the grain size of the diffusion solid solution layer is 40nm, the thickness of a strontium titanate layer is 43nm, the grain size of the strontium titanate layer is 50nm, the bonding force of the calcium film and a copper foil is 5B, the bonding force of the calcium film and a ceramic film is 5B, the minimum bending radius of the flexible energy storage film is 2mm, the breakdown field strength is 2000kV/cm, and the energy storage density is 40J/cm3After 1000 times of bending, the bonding force between layers is 5B, and the energy storage density is 40J/cm3The retention rate is 100%, and the method can be applied to film capacitors.
Example 3:
using flexible aluminum foil as substrate, thickness of 12 micrometer and surface roughness of 0.7 micrometer, placing in vacuum chamber, and vacuumizing to 3 × 10-3Pa. And heating the vacuum chamber to 250 ℃, keeping the temperature for 20min, filling argon, controlling the flow of the argon to be 30sccm, opening the Hall ion source, setting the voltage of the Hall ion source to be 1000v and the current to be 0.5A, and treating for 5min to enable the surface tension of the aluminum foil to reach 75 dynes.
Closing the gate valve to a vacuum degree of 2.0X 10-2And Pa, keeping the flow of argon at 30sccm, turning on a magnetic filtration multi-arc ion plating power supply, adjusting the arc current to 60A, leading out a current of 9A, applying a bias voltage of 7V to the flexible aluminum foil, taking the barium target as a metal simple substance target material, depositing for 120s, and forming a 80nm barium film on the copper foil.
And (2) closing a magnetic filtration multi-arc ion plating power supply, opening the flow of large argon to 110sccm to enable the vacuum degree of a vacuum chamber to be 0.4Pa, opening a magnetron sputtering power supply to 120W, taking strontium titanate with the density of 97% as a target material, depositing for 1min, and forming a 50nm strontium titanate prefabricated layer on the metal film, wherein the grain size of the strontium titanate prefabricated layer is 20nm, the structure is compact, and the structure of the flexible energy storage film is shown as a in figure 1.
And (2) closing the magnetron sputtering power supply, opening the heating power supply, setting the argon flow to be 150sccm, the vacuum degree to be 0.5Pa, the heating temperature to be 400 ℃, keeping the temperature for 300min, and diffusing barium atoms in the barium film to the strontium titanate prefabricated layer to obtain a ceramic film, wherein the ceramic film comprises a barium-doped strontium titanate diffusion solid solution layer and a strontium titanate layer which are sequentially attached to the barium film, and the specific structure is shown as b in the figure 1.
And depositing silver metal on the strontium titanate layer of the flexible energy storage film shown in the b in the figure 1 as an upper electrode through a magnetron sputtering process, and carrying out an electrical property test.
Tests show that the thickness of a barium film in the obtained flexible energy storage film is 70nm, the thickness of a diffusion solid solution layer is 10nm, the grain size of the diffusion solid solution layer is 85nm, the thickness of a strontium titanate layer is 37nm, the grain size of the strontium titanate layer is 100nm, the bonding force of the barium film and a copper foil is 5B, the bonding force of the barium film and a ceramic film is 5B, and the minimum bending radius of the flexible energy storage film is 8mm,the breakdown field strength is 3000kV/cm, and the energy storage density is 55J/cm3After 1000 times of bending, the bonding force between layers is 5B, and the energy storage density is 55J/cm3The retention rate is 100%, and the method can be applied to film capacitors.
Example 4:
placing flexible gold foil as substrate with thickness of 18 μm and surface roughness of 0.5 μm in vacuum chamber, and vacuumizing to 3 × 10-3Pa. Heating the vacuum chamber to 250 ℃, keeping the temperature for 10min, filling argon, controlling the argon flow to be 30sccm, opening the Hall ion source, setting the voltage of the Hall ion source to be 1000v and the current to be 0.5A, and treating for 10min to enable the surface tension of the gold foil to reach 75 dynes.
Closing the gate valve to a vacuum degree of 2.0X 10-2Pa, keeping the flow of argon gas at 30sccm, turning on a magnetic filtration multi-arc ion plating power supply, adjusting the arc current to 60A, leading out current 10A, applying bias voltage of 8V on the flexible gold foil, taking a lead target as a metal simple substance target material, depositing for 90s, and forming a 60nm lead film on the copper foil.
And (2) closing a magnetic filtration multi-arc ion plating power supply, opening the flow of large argon to 100sccm to enable the vacuum degree of the vacuum chamber to be 0.4Pa, opening a magnetron sputtering power supply to 150W, taking strontium titanate with the density of 98% as a target material, depositing for 2min, and forming a 110nm strontium titanate prefabricated layer on the metal film, wherein the grain size of the strontium titanate prefabricated layer is 300nm, the structure is compact, and the structure of the flexible energy storage film is shown as a in figure 1.
And (3) closing the magnetron sputtering power supply, opening the heating power supply, setting the argon flow to be 200sccm, the vacuum degree to be 1Pa, the heating temperature to be 500 ℃, and keeping the temperature for 120min to diffuse lead atoms in the lead film to the strontium titanate prefabricated layer to obtain a ceramic film, wherein the ceramic film comprises a lead-doped strontium titanate diffusion solid solution layer and a strontium titanate layer which are sequentially attached to the lead film, and the specific structure is shown as b in the figure 1.
And (3) depositing platinum metal on the strontium titanate layer of the flexible energy storage film shown in the b in the figure 1 as an upper electrode through a magnetron sputtering process, and performing an electrical property test.
The thickness of the lead film in the obtained flexible energy storage film is tested to be50nm, the thickness of the diffusion solid solution layer is 10nm, the grain size of the diffusion solid solution layer is 300nm, the thickness of the strontium titanate layer is 95nm, the grain size of the strontium titanate layer is 400nm, the bonding force between the lead film and the copper foil is 5B, the bonding force between the lead film and the ceramic film is 5B, the minimum bending radius of the flexible energy storage film is 10mm, the breakdown field strength is 2800kV/cm, and the energy storage density is 50J/cm3After 1000 times of bending, the bonding force between layers is 5B, and the energy storage density is 50J/cm3The retention rate is 100%, and the method can be applied to film capacitors.
Example 5:
using flexible platinum foil as substrate, thickness of 12 micrometers and surface roughness of 0.8 micrometers, placing in vacuum chamber, vacuumizing to 3X 10-3Pa. Heating the vacuum chamber to 300 ℃, keeping the temperature for 20min, filling argon gas, controlling the argon gas flow to be 30sccm, opening the Hall ion source, setting the voltage of the Hall ion source to be 1500v and the current to be 0.5A, and treating for 20min to enable the surface tension of the foil platinum to reach 80 dynes.
Closing the gate valve to a vacuum degree of 2.0X 10-2Pa, keeping the flow of argon gas at 30sccm, turning on a magnetic filtration multi-arc ion plating power supply, adjusting the arc current to 60A, leading out a current of 7A, applying a bias voltage of 6V on the flexible platinum foil, taking a strontium target as a metal simple substance target material, depositing for 180s, and forming a 100nm strontium film on the copper foil.
Turning off a magnetic filtration multi-arc ion plating power supply, turning on the flow of large argon to 120sccm, enabling the vacuum degree of a vacuum chamber to be 0.5Pa, turning on a magnetron sputtering power supply to 120W, taking strontium titanate with the density of 98% as a target material, depositing for 10min, forming a 500nm strontium titanate prefabricated layer on the metal film, wherein the grain size of the strontium titanate prefabricated layer is 250nm, the structure is compact, and the structure of the flexible energy storage film is shown as a in figure 1.
And (2) closing the magnetron sputtering power supply, opening the heating power supply, setting the argon flow to be 180sccm, the vacuum degree to be 0.7Pa, the heating temperature to be 400 ℃, keeping the temperature for 60min, and diffusing strontium atoms in the strontium thin film to the strontium titanate prefabricated layer to obtain the ceramic thin film, wherein the ceramic thin film comprises a diffusion solid solution layer and a strontium titanate layer which are sequentially attached to the strontium thin film and have non-stoichiometric ratio, and the specific structure is shown as b in figure 1.
And (3) depositing platinum metal on the strontium titanate layer of the flexible energy storage film shown in the b in the figure 1 as an upper electrode through a magnetron sputtering process, and performing an electrical property test.
Tests prove that the thickness of a strontium film in the obtained flexible energy storage film is 95nm, the thickness of a diffusion solid solution layer is 10nm, the grain size of the diffusion solid solution layer is 200nm, the thickness of a strontium titanate layer is 400nm, the grain size of the strontium titanate layer is 300nm, the bonding force of the strontium film and a copper foil is 5B, the bonding force of the strontium film and a ceramic film is 5B, the minimum bending radius of the flexible energy storage film is 4mm, the breakdown field strength is 2600kV/cm, and the energy storage density is 40J/cm3After 1000 times of bending, the bonding force between layers is 5B, and the energy storage density is 40J/cm3The retention rate is 100%, and the method can be applied to film capacitors.
Example 6
Using flexible electrolytic copper foil as substrate, thickness of 12 micrometer and surface roughness of 0.8 micrometer, placing in vacuum chamber, and vacuumizing to 3 × 10-3Pa. And heating the vacuum chamber to 400 ℃, keeping the temperature for 20min, introducing argon gas, controlling the flow of the argon gas to be 30sccm, opening the Hall ion source, setting the voltage of the Hall ion source to be 1200v and the current to be 0.5A, and treating for 20min to ensure that the surface tension of the electrolytic copper foil reaches 70 dynes.
Closing the gate valve to a vacuum degree of 2.0X 10-2Pa, keeping the flow of argon gas at 10sccm, turning on a magnetic filtration multi-arc ion plating power supply, adjusting the arc current to 45A, leading out a current of 11A, applying a bias voltage of 5V on the flexible electrolytic copper foil, taking a strontium target as a metal simple substance target material, depositing for 120s, and forming a 80nm strontium film on the copper foil.
Turning off a magnetic filtration multi-arc ion plating power supply, turning on the flow of large argon to 30sccm, enabling the vacuum degree of a vacuum chamber to be 0.1Pa, turning on a magnetron sputtering power supply to 200W, taking strontium titanate with the density of 96% as a target material, depositing for 60min, and forming a strontium titanate prefabricated layer with the grain size of 3 mu m on the metal film, wherein the grain size of the strontium titanate prefabricated layer is 450nm, the structure is compact, and the structure of the flexible energy storage film is shown as a in figure 1.
And (2) closing the magnetron sputtering power supply, opening the heating power supply, setting the argon flow to be 200sccm, the vacuum degree to be 0.7Pa, the heating temperature to be 400 ℃, keeping the temperature for 300min, and diffusing strontium atoms in the strontium thin film to the strontium titanate prefabricated layer to obtain the ceramic thin film, wherein the ceramic thin film comprises a diffusion solid solution layer and a strontium titanate layer which are sequentially attached to the strontium thin film and have non-stoichiometric ratio, and the specific structure is shown as b in figure 1.
And (3) depositing platinum metal on the strontium titanate layer of the flexible energy storage film shown in the b in the figure 1 as an upper electrode through a magnetron sputtering process, and performing an electrical property test.
Tests prove that the thickness of a strontium film in the obtained flexible energy storage film is 70nm, the thickness of a diffusion solid solution layer is 7nm, the grain size of the diffusion solid solution layer is 240nm, the thickness of a strontium titanate layer is 2 mu m, the grain size of the strontium titanate layer is 500nm, the bonding force of the strontium film and a copper foil is 5B, the bonding force of the strontium film and a ceramic film is 5B, the minimum bending radius of the flexible energy storage film is 15mm, the breakdown field strength is 1000kV/cm, and the energy storage density is 12J/cm3After 1000 times of bending, the bonding force between layers is 5B, and the energy storage density is 12J/cm3The retention rate is 100%, and the method can be applied to film capacitors.
Example 7
Using flexible electrolytic copper foil as substrate, thickness of 12 micrometer and surface roughness of 0.8 micrometer, placing in vacuum chamber, and vacuumizing to 3 × 10-3Pa. And heating the vacuum chamber to 400 ℃, keeping the temperature for 20min, introducing argon gas, controlling the flow of the argon gas to be 30sccm, opening the Hall ion source, setting the voltage of the Hall ion source to be 1200v and the current to be 0.5A, and treating for 20min to ensure that the surface tension of the electrolytic copper foil reaches 70 dynes.
Closing the gate valve to a vacuum degree of 4.0 × 10-2Pa, keeping the flow of argon gas at 40sccm, turning on a magnetic filtration multi-arc ion plating power supply, adjusting the arc current to 45A, leading out a current of 11A, applying a bias voltage of 6V on the flexible electrolytic copper foil, taking a strontium target as a metal simple substance target material, depositing for 30s, and forming a 18nm strontium film on the copper foil.
And (2) closing a magnetic filtration multi-arc ion plating power supply, opening the flow of large argon to 80sccm to enable the vacuum degree of the vacuum chamber to be 0.4Pa, opening a magnetron sputtering power supply to 50W, taking strontium titanate with the density of 96% as a target material, depositing for 60min, and forming a strontium titanate prefabricated layer with the grain size of 1 mu m on the metal film, wherein the crystal grain size of the strontium titanate prefabricated layer is 350nm, the structure is compact, and the structure of the flexible energy storage film is shown as a in figure 1.
And (2) closing the magnetron sputtering power supply, opening the heating power supply, setting the argon flow to be 200sccm, the vacuum degree to be 0.7Pa, the heating temperature to be 400 ℃, keeping the temperature for 300min, and diffusing strontium atoms in the strontium thin film to the strontium titanate prefabricated layer to obtain the ceramic thin film, wherein the ceramic thin film comprises a diffusion solid solution layer and a strontium titanate layer which are sequentially attached to the strontium thin film and have non-stoichiometric ratio, and the specific structure is shown as b in figure 1.
And (3) depositing platinum metal on the strontium titanate layer of the flexible energy storage film shown in the b in the figure 1 as an upper electrode through a magnetron sputtering process, and performing an electrical property test.
Tests prove that the thickness of a strontium film in the obtained flexible energy storage film is 10nm, the thickness of a diffusion solid solution layer is 7nm, the grain size of the diffusion solid solution layer is 240nm, the thickness of a strontium titanate layer is 0.9 mu m, the grain size of the strontium titanate layer is 400nm, the bonding force of the strontium film and a copper foil is 5B, the bonding force of the strontium film and a ceramic film is 5B, the minimum bending radius of the flexible energy storage film is 13mm, the breakdown field strength is 1500kV/cm, and the energy storage density is 15J/cm3After 1000 times of bending, the bonding force between layers is 5B, and the energy storage density is 15J/cm3The retention rate is 100%, and the method can be applied to film capacitors.
Comparative example 1
Comparative example 1 is different from example 1 only in that comparative example 1 forms a strontium thin film and a strontium titanate preform layer by a magnetron sputtering method.
Tests prove that the thickness of the strontium film in the obtained flexible energy storage film is 5nm, the thickness of the diffusion solid solution layer is 5nm, the grain size of the diffusion solid solution layer is 20nm, the thickness of the strontium titanate layer is 10nm, the grain size of the strontium titanate layer is 30nm, the bonding force of the strontium film and the copper foil is 4B, the bonding force of the strontium film and the ceramic film is 5B, and the flexibility energy storage film is flexibleThe minimum bending radius of the linear energy storage film is 4mm, the breakdown field strength is 1800kV/cm, and the energy storage density is 30J/cm3After 1000 times of bending, the bonding force of the strontium film and the copper foil is 3B, the bonding force of the strontium film and the ceramic film is 5B, and the energy storage density is 20J/cm3The retention ratio was 66.7%.
Comparative example 2:
comparative example 2 is different from example 1 only in that comparative example 2 forms a titanium thin film on a copper foil using a titanium target as a metal simple substance target.
Tests prove that the thickness of a titanium film in the obtained flexible energy storage film is 5nm, the thickness of a diffusion solid solution layer is 5nm, the size of the diffusion solid solution layer is 20nm, the thickness of a strontium titanate layer is 10nm, the grain size of the strontium titanate layer is 30nm, the bonding force of the titanium film and a copper foil is 4B, the bonding force of the titanium film and a ceramic film is 4B, the minimum bending radius of the flexible energy storage film is 4mm, the breakdown field strength is 900kV/cm, and the energy storage density is 6J/cm3After 1000 times of bending, the bonding force between the titanium film and the copper foil is 3B, the bonding force between the titanium film and the ceramic film is 3B, and the energy storage density is 3J/cm3The retention ratio was 50%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. The flexible energy storage thin film is characterized by comprising a flexible metal substrate, and a metal thin film and a strontium titanate layer which are sequentially formed on the flexible metal substrate;
the surface of the strontium titanate layer, which is attached to the metal film, is a diffusion solid solution layer which is formed by diffusing metal atoms in the metal film to the strontium titanate layer to realize doping, the metal film is one of a strontium film, a calcium film, a barium film and a lead film, and the metal atoms in the diffusion solid solution layer are one of strontium, calcium, barium and lead.
2. The flexible energy storage film of claim 1, wherein the metal film has a thickness of 5nm to 95 nm.
3. The flexible energy storage thin film according to claim 1, wherein the thickness of the strontium titanate layer is 10nm to 2 μm, and the grain size is 30nm to 500 nm.
4. The flexible energy storage film of claim 1, wherein the thickness of the diffusive solid solution layer is 5nm to 10nm, and the grain size is 20nm to 300 nm.
5. The flexible energy storage film of claim 1, wherein the flexible metal substrate has a thickness of 12 μm to 18 μm.
6. The flexible energy storage film of claim 1, wherein the surface roughness of the flexible metal substrate is 0.4 μ ι η to 0.8 μ ι η.
7. The flexible energy storage film of claim 1, wherein the surface tension of the flexible metal substrate is greater than or equal to 60 dynes.
8. The flexible energy storage film of claim 1, wherein the flexible metal substrate comprises one of a copper foil, a titanium foil, a silver foil, a gold foil, a platinum foil, an aluminum foil, a nickel foil, a chromium foil, and a tin foil.
9. The flexible energy storage film of claim 1, wherein the flexible energy storage film has a minimum bend radius of 2mm to 15 mm; and/or
The breakdown field strength of the flexible energy storage film is 1000 kV/cm-3000 kV/cm; and/or
The energy storage density of the flexible energy storage film is 12J/cm3～55J/cm3(ii) a And/or
The adhesive force between the metal film and the flexible metal substrate is 5B; and/or
And the adhesion force between the diffusion solid solution layer and the metal film is 5B.
CN201811196365.0A 2018-07-25 2018-07-25 Flexible energy storage film Active CN110767473B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811196365.0A CN110767473B (en) 2018-07-25 2018-07-25 Flexible energy storage film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810829730.0A CN110767472B (en) 2018-07-25 2018-07-25 Flexible energy storage film, preparation method thereof and film capacitor
CN201811196365.0A CN110767473B (en) 2018-07-25 2018-07-25 Flexible energy storage film

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201810829730.0A Division CN110767472B (en) 2018-07-25 2018-07-25 Flexible energy storage film, preparation method thereof and film capacitor

Publications (2)

Publication Number Publication Date
CN110767473A CN110767473A (en) 2020-02-07
CN110767473B true CN110767473B (en) 2022-06-03

Family

ID=69328145

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201810829730.0A Active CN110767472B (en) 2018-07-25 2018-07-25 Flexible energy storage film, preparation method thereof and film capacitor
CN201811196365.0A Active CN110767473B (en) 2018-07-25 2018-07-25 Flexible energy storage film

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201810829730.0A Active CN110767472B (en) 2018-07-25 2018-07-25 Flexible energy storage film, preparation method thereof and film capacitor

Country Status (1)

Country Link
CN (2) CN110767472B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001127255A (en) * 1999-10-29 2001-05-11 Kyocera Corp Thin film electronic component
WO2005080074A1 (en) * 2004-02-19 2005-09-01 Hitachi Chemical Co., Ltd. Thin film composite material, method for producing same, and multilayer wiring board and electronic component using such thin film composite material
CN105742060A (en) * 2016-03-31 2016-07-06 同济大学 High-energy-storage-density solid-state thin film integrated circuit capacitor and preparation method therefor
CN106935398A (en) * 2017-03-24 2017-07-07 同济大学 A kind of bismuth strontium titanate doping thin film capacitor and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040175585A1 (en) * 2003-03-05 2004-09-09 Qin Zou Barium strontium titanate containing multilayer structures on metal foils
JP2014154632A (en) * 2013-02-06 2014-08-25 Rohm Co Ltd Multilayer structure, capacitor element, and method of manufacturing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001127255A (en) * 1999-10-29 2001-05-11 Kyocera Corp Thin film electronic component
WO2005080074A1 (en) * 2004-02-19 2005-09-01 Hitachi Chemical Co., Ltd. Thin film composite material, method for producing same, and multilayer wiring board and electronic component using such thin film composite material
CN105742060A (en) * 2016-03-31 2016-07-06 同济大学 High-energy-storage-density solid-state thin film integrated circuit capacitor and preparation method therefor
CN106935398A (en) * 2017-03-24 2017-07-07 同济大学 A kind of bismuth strontium titanate doping thin film capacitor and preparation method thereof

Also Published As

Publication number Publication date
CN110767473A (en) 2020-02-07
CN110767472A (en) 2020-02-07
CN110767472B (en) 2022-03-25

Similar Documents

Publication Publication Date Title
CN110660583B (en) Thin film capacitor
JP4225081B2 (en) Electronic component manufacturing method, electronic component, and surface acoustic wave filter
CN204809042U (en) Anti -oxidant capacitor film
WO2023284596A1 (en) High-conductivity, corrosion-resistant and long-lifetime max phase solid solution composite coating, and preparation method therefor and use thereof
CN112993143B (en) Electret (electret)
CN102543430A (en) Pyrochlore film multilayer ceramic capacitor and low-temperature preparation method thereof
CN110767450B (en) Thin film capacitor
CN110767473B (en) Flexible energy storage film
TW200923987A (en) High-capacitance density thin-film dielectrics having columnar grains formed on base-metal foils
JPH08236105A (en) Manufacture of lithium secondary battery positive electrode
JP2778091B2 (en) Metallized film for capacitor and method of manufacturing the same
CN110767447B (en) Flexible energy storage film, preparation method thereof and film capacitor
Agawane et al. Investigations on chemo-mechano stabilities of the molybdenum thin films deposited by DC-sputter technique
JP2002217213A (en) Manufacturing method for compound-semiconductor thin- film
CN108735825A (en) Back electrode of solar cell and solar cell and preparation method thereof
JP6156246B2 (en) Method for producing solid electrolyte-electrode composite
JP2007242880A (en) Film deposition method
KR101462498B1 (en) Fabrication Method of CIGS Absorber Layers and its application to Thin Film Solar Cells
US4089990A (en) Battery plate and method of making
WO2024207173A1 (en) Copper interconnect structure system and preparation method therefor, and electronic component
CN114540767B (en) Preparation method of flexible aluminum electrode film
CN117049597B (en) Preparation method of high-energy-ratio dielectric capacitor and dielectric capacitor
CN107887161A (en) Antidamping capacitor film
KR101831700B1 (en) Fabrication method of cigs absorber layer and thin film solar cell using double intrelayers and thin film solar cell
JP7015673B2 (en) Power storage device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant