CN110660584B - Preparation method of flexible energy storage film - Google Patents

Preparation method of flexible energy storage film Download PDF

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CN110660584B
CN110660584B CN201811611926.9A CN201811611926A CN110660584B CN 110660584 B CN110660584 B CN 110660584B CN 201811611926 A CN201811611926 A CN 201811611926A CN 110660584 B CN110660584 B CN 110660584B
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strontium titanate
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metal substrate
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CN110660584A (en
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冯雪
王志建
陈颖
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Tsinghua University
Institute of Flexible Electronics Technology of THU Zhejiang
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Institute of Flexible Electronics Technology of THU Zhejiang
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    • 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
    • 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
    • C23C14/22—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
    • 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
    • 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
    • H01G4/005—Electrodes
    • 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 
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    • 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

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Abstract

The invention relates to a preparation method of a flexible energy storage film. The preparation method comprises the following steps: providing a flexible metal substrate; depositing a strontium titanate film prefabricated layer on the flexible metal substrate; and carrying out heat treatment on the flexible metal substrate with the strontium titanate film prefabricated layer to obtain a strontium titanate layer, thereby obtaining the flexible energy storage film. The energy storage film is made of strontium titanate material, and the flexibility of the energy storage film is realized through the preparation method. Meanwhile, the prepared energy storage film has high dielectric constant, low dielectric loss, high breakdown field strength and high energy storage density, and can be used as a dielectric material of a film capacitor.

Description

Preparation method of flexible energy storage film
The application is "the application number is: 201810713410.9, the application date is 29 days of 2018, 6 months, and the invention name is: flexible energy storage film, preparation method thereof and divisional application of film capacitor.
Technical Field
The invention relates to the field of energy, in particular to a preparation method of a flexible energy storage film.
Background
With the trend of miniaturization, multifunction, light and thin electronic devices, the trend of miniaturization, light and thin electronic devices, high integration, and multifunction is also required.
For thin film capacitors, a desirable way to achieve miniaturization is to increase the dielectric constant of the dielectric thin film to increase the capacitance. The dielectric film mainly comprises a high polymer energy storage film and a ceramic energy storage film, and in the traditional film capacitor, the dielectric film mainly comprises the high polymer energy storage film. Because the dielectric constant of the ceramic energy storage film is far higher than that of the high polymer energy storage film, the use of the ceramic energy storage film to replace the high polymer energy storage film accords with the development trend of the film capacitor. However, ceramic energy storage films lack the flexibility of polymeric energy storage films.
Disclosure of Invention
Based on the above, it is necessary to provide a method for preparing 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 ensures that the energy storage film has high dielectric constant, low dielectric loss, high breakdown field strength and high energy storage density, and can be used as a dielectric material of a film capacitor.
A preparation method of a flexible energy storage film comprises the following steps:
providing a flexible metal substrate;
depositing a strontium titanate film prefabricated layer on the flexible metal substrate;
and carrying out heat treatment on the flexible metal substrate with the strontium titanate film prefabricated layer to obtain a strontium titanate layer, thereby obtaining the flexible energy storage film.
In one embodiment, strontium titanate is used as a target material, and a magnetron sputtering method is adopted to deposit and form a strontium titanate thin film prefabricated layer on the flexible metal substrate.
In one embodiment, the power of the magnetron sputtering is 50-200W, and the deposition time is 1-60 minutes.
In one embodiment, the working atmosphere of the magnetron sputtering is argon, the flow rate of the argon is 30 sccm-120 sccm, and the vacuum degree is 0.1 Pa-0.5 Pa.
In one embodiment, the thickness of the strontium titanate thin film preformed layer is 30 nm-3 μm, and the grain size is 10 nm-450 nm.
In one embodiment, oxygen is introduced during the heat treatment, the flow rate of the oxygen is 30sccm to 150sccm, and the vacuum degree is 0.1Pa to 1Pa.
In one embodiment, the heat treatment is performed at a temperature of 300 ℃ to 600 ℃ for 20 minutes to 60 minutes.
In one embodiment, the thickness of the flexible metal substrate is 12-18 μm; and/or
The surface roughness of the flexible metal substrate is 0.4-0.8 mu m; and/or
The surface tension of the flexible metal substrate is more than or equal to 60 dynes; and/or
The flexible metal substrate includes a copper foil.
The invention adopts the flexible metal substrate, and forms the strontium titanate film on the flexible metal substrate, thereby realizing the flexibility of the ceramic energy storage film and having high preparation efficiency. Meanwhile, the prepared energy storage film has high dielectric constant, low dielectric loss, high breakdown field strength and high energy storage density, and can be used as a dielectric material of a film capacitor.
Drawings
FIG. 1 is a flow chart of a process for preparing a flexible energy storage film according to the present invention, wherein (a) is a flexible metal substrate, (b, c) is a strontium titanate film formed on the flexible metal substrate, and (d) is an electrode layer formed on the strontium titanate film;
fig. 2 is a schematic diagram of the energy storage films of example 1, example 10 and comparative example 1 according to the present invention, in which (g) is the flexible energy storage film of example 1, (f) is the flexible energy storage film of example 10, and (e) is the strontium titanate energy storage film of comparative example 1.
Detailed Description
The method for preparing the flexible energy storage film provided by the invention is further described below.
As shown in fig. 1, the preparation method of the flexible energy storage film provided by the invention comprises the following steps:
(a) Providing a flexible metal substrate;
(b) Taking strontium titanate as a target material, and depositing and forming a strontium titanate film prefabricated layer on the flexible metal substrate by adopting a magnetron sputtering method;
(c) Performing heat treatment on the flexible metal substrate deposited with the strontium titanate film prefabricated layer to obtain a strontium titanate film; and
(d) And forming an electrode layer on the strontium titanate film to obtain the flexible energy storage film.
In the step (a), the material of the flexible metal substrate is not limited as long as it has good flexibility, strong oxidation resistance at high temperature, conductivity, and no reaction with the ceramic thin film, including one of Pt, au, ag, cu, ni, ti, al.
Considering that copper foil is the most cost-effective metal material in the electronics industry, its resistivity is 1.75X10 -8 Omega.m, next to silver (1.65X10) -8 Ω·m), a thermal conductivity 401W/(m·K), inferior to silver (420W/(m·K)), and a price of copper is far 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 no oxidation is generated when the rolled copper foil and the electrolytic copper foil are calcined in air at 400-500 ℃. Therefore, the flexible metal substrate is preferably copper foil.
Further, the rolled copper foil is composed of rod-shaped crystal grains parallel to the surface of the copper foil, has excellent bending resistance, and the electrolytic copper foil is composed of rod-shaped crystal grains perpendicular to the surface of the copper foil, and has bending resistance lower than that of the rolled copper foil, so that the copper foil is preferably a rolled copper foil.
The thinner the flexible substrate is, the better the flexibility is, and therefore, the thickness of the flexible substrate is 12 μm to 18 μm, and more preferably, a rolled copper foil of 12 μm is used.
In the thin film capacitor, the flexible substrate is used as an electrode, the actual contact area of the strontium titanate film and the electrode is related to the surface roughness of the flexible substrate, and the larger the surface roughness is, the larger the actual contact area is, and the larger the capacitance value of the unit geometric area is. However, the surface roughness of the flexible substrate is too large, which easily causes holes on the surface of the strontium titanate film to affect the energy storage performance of the flexible energy storage film. Therefore, the surface roughness of the flexible substrate is 0.4 μm to 0.8 μm.
The surface tension of the flexible substrate is more than or equal to 60 dynes, preferably more than 60 dynes, and the higher the surface tension of the flexible substrate is, the stronger the binding force between the strontium titanate film and the flexible substrate is.
The surface tension can be increased by treating the surface of the flexible substrate to increase the surface activity. Preferably, the method of the treatment comprises the following steps: heating the flexible substrate, setting the temperature to be 100-300 ℃, preserving the temperature for 10-30 minutes, and then adopting a Hall ion source to treat the flexible substrate, wherein the voltage of the Hall ion source is 800-2000V, the current is 0.5-2A, and the treatment time is 1-10 minutes.
In the step (b), a magnetron sputtering process is adopted to deposit and form a strontium titanate film prefabricated layer on the flexible metal substrate. The strontium titanate target is bombarded by ions which move spirally at high speed under the action of an electric field and a magnetic field, and atoms or ion groups bombarded from the strontium titanate target are deposited on the flexible metal substrate to form a strontium titanate film prefabricated layer. The magnetron sputtering particles have the energy of 1eV to 10eV, and the surface mobility of the flexible metal substrate can be kept high, so that the formed strontium titanate film prefabricated layer has good crystallization performance, high deposition efficiency, low temperature of the flexible metal substrate required for forming the strontium titanate film prefabricated layer and good compatibility with an integration process.
Compared with PLD, sol-gel, hydrothermal method and the like, the method for depositing the strontium titanate film prefabricated layer on the flexible metal substrate by adopting 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, oxygen cooling protection is not needed at the end of film forming, and the flexible metal substrate is protected from being oxidized, so that the flexible metal substrate has high conductivity.
If the compactness of the strontium titanate target is not high, the surface and the internal air holes of the strontium titanate target are relatively 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 are expanded to lead the strontium titanate target to crack. Therefore, the compactness of the strontium titanate target material is preferably more than or equal to 96 percent, more preferably more than 96 percent, so that the target material is convenient for magnetron sputtering and stable in work.
In the magnetron sputtering process, the working atmosphere of the magnetron sputtering is argon, the flow of the argon is 30 sccm-120 sccm, and the vacuum degree is 0.1 Pa-0.5 Pa. The power of the magnetron sputtering is 50-200W, and the deposition time is 1-60 minutes.
Further, the thickness of the deposited strontium titanate film prefabricated layer is 30 nm-3 mu m, the grain size is 10 nm-450 nm, and the film structure is compact.
In step (c), the flexible metal substrate on which the strontium titanate thin film preform layer is deposited is subjected to a heat treatment, which is an annealing heat treatment. SrTiO when annealing at 300-400 DEG C 3 The Sr, ti and O atoms in the ceramic can exchange energy by means of lattice vibration, and some atoms in distorted positions can be restored to normal states, so that the internal stress is correspondingly reduced. At 400-500 c annealing, the mobility of Sr, ti and O atoms increases, so that some vacancies, interstitial atoms and dislocations that were originally "frozen" will recombine within the film, or migrate to the surface and grain boundaries to disappear, or combine into a lower energy defect configuration (e.g., dislocation loops, vacancy clusters, etc.). In this case, the internal stress of the film will be greatly reduced. When annealing is carried out at 500-600 ℃, the diffusion of Sr, ti and O atoms is aggravated, besides the freezing defect can be further eliminated, various recrystalization can also occur, thereby reducing the grain boundary and further obviously reducing the internal stress of the film. Preferably, the temperature of the heat treatment of the invention is 300-600 ℃ and the time is 20-60 minutes. By adopting annealing heat treatments with different temperatures and times, the non-equilibrium defects such as lattice mismatch, lattice reconstruction, impurities, phase change and the like in the strontium titanate film prefabricated layer disappear greatly, and the strontium titanate film is obtained. Compared with the strontium titanate film prefabricated layer, the internal stress of the strontium titanate film is obviously reduced.
Preferably, oxygen is filled during the heat treatment, the flow rate of the oxygen is 30sccm to 150sccm, and the vacuum degree is 0.1Pa to 1Pa. Oxygen can eliminate oxygen vacancies of the strontium titanate ceramic film in the deposition process, and further reduce defects of the strontium titanate ceramic film.
In the step (d), the electrode layer may be formed by deposition through a magnetron sputtering process, that is, the electrode layer is formed on the strontium titanate thin film by deposition again using the magnetron sputtering process after the heat treatment, and the working efficiency is high.
Considering that the thinner the electrode layer is, the higher the sheet resistance of the electrode layer is, and correspondingly, the higher the voltage resistance of the electrode layer is; the thicker the electrode layer, the lower the sheet resistance of the electrode layer, and correspondingly, the higher the current resistance of the electrode layer. Moreover, the thinner the electrode layer is, the more easily oxidized, resulting in capacity disappearance; and the thicker the electrode layer, the lower the withstand voltage capability of the electrode layer, resulting in the electrode layer being easily broken down. Preferably, the thickness of the electrode layer is 100 nm-3 μm, and the sheet resistance of the electrode layer is 0.001mΩ/≡0.5 Ω/≡.
Preferably, the material of the electrode layer includes at least one of copper, platinum, gold, silver, and aluminum, and more preferably copper.
The invention adopts the flexible metal substrate, forms the strontium titanate film on the flexible metal substrate through the magnetron sputtering process, and then forms the electrode layer on the strontium titanate film to form the ceramic energy storage film, thereby not only realizing the flexibility of the ceramic energy storage film, but also having high preparation efficiency, good crystallinity, grain size and other microstructures of the strontium titanate film, low internal stress and improving the energy storage performance of the flexible energy storage film.
The invention also provides a flexible energy storage film, which comprises a flexible metal substrate, and a strontium titanate film and an electrode layer which are sequentially formed on the flexible metal substrate.
The thickness of the strontium titanate film is 10 nm-2 mu m, and the grain size is 30-500 nm; the thickness of the electrode layer is 100 nm-3 mu m.
The flexible metal substrate comprises a copper foil, wherein the thickness of the copper foil is 12-18 mu m; and/or
The surface roughness of the copper foil is 0.4-0.8 mu m; and/or
The surface tension of the copper foil is more than or equal to 60 dynes.
The minimum bending radius of the flexible energy storage film is 2 mm-20 mm; and/or
The dielectric constant of the flexible energy storage film is 280-310; and/or
The dielectric loss of the flexible energy storage film is 0.003-0.05; and/or
The breakdown field intensity 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/cm 3 ～55J/cm 3 。
The energy storage film is composed of the flexible metal substrate, the strontium titanate material and the electrode layer, so that the flexibility of the energy storage film is realized, and the energy storage film has high dielectric constant, low dielectric loss, high breakdown field strength and high energy storage density.
The invention also provides a thin film capacitor comprising the flexible energy storage thin film.
The flexible energy storage film of the invention can be used for replacing a high polymer film, and the trend development of the film capacitor towards miniaturization, light weight, high integration and multifunction can be promoted. Meanwhile, the film capacitor has the advantages of no polarity, high insulation impedance, excellent frequency characteristic (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 railway, new energy automobiles, wind power generation, solar power generation and the like. Particularly, in the signal connecting part, the film capacitor with good frequency characteristic and low dielectric loss can ensure that the signal is not too much distorted during transmission, and has good electrical performance and high reliability.
Hereinafter, the method for preparing the flexible energy storage film will be further described by the following specific examples.
Example 1:
as shown in FIG. 1, a rolled copper foil was used as a substrate, the thickness of the copper foil was 18. Mu.m, the surface roughness was 0.5. Mu.m, and the substrate was placed in a vacuum chamber and evacuated to 3X 10 -3 Pa. The vacuum chamber is heated to 150 ℃ and kept for 10min, argon is filled, and the flow rate of the argon is 30sccm. Opening a Hall ion source, setting the voltage of the Hall ion source to be 1000v, and electrifyingThe flow was 0.5A and the treatment was carried out for 1min to bring the surface tension of the copper foil to 60 dynes.
Closing the gate valve until the vacuum degree is 0.4Pa, keeping the argon flow at 30sccm, starting a magnetron sputtering power supply to 80w, taking 96% of strontium titanate with the density as a target material, depositing for 3 minutes, and forming a 130nm strontium titanate film prefabricated layer on the copper foil, wherein the grain size of the strontium titanate film prefabricated layer is 80nm, and the structure is compact.
Closing argon, filling oxygen, ensuring the vacuum degree to be 0.1Pa, setting the heating temperature to 300 ℃, and keeping the temperature for 30min, wherein the oxygen flow is 30sccm.
Closing an oxygen valve, opening an argon valve, ensuring the vacuum degree to be 0.4Pa, opening a magnetron sputtering power supply, setting the magnetron sputtering current 4A, taking metal copper as a target material, depositing for 10 minutes to form a copper electrode layer, wherein the thickness of the copper electrode layer is 100nm, and the sheet resistance is 0.5 omega/≡, so that the flexible energy storage film shown in (g) in fig. 2 is obtained.
Through tests, the thickness of the strontium titanate film in the obtained flexible energy storage film is 100nm, the minimum bending radius of the flexible energy storage film is 4mm, the grain size is 120nm, the dielectric constant is 300, the dielectric loss is 0.008, the breakdown field strength is 1800kV/cm, and the energy storage density is 30J/cm 3 Can be applied to film capacitors.
Example 2:
as shown in FIG. 1, a rolled copper foil having a thickness of 12 μm and a surface roughness of 0.5 μm was used as a substrate, placed in a vacuum chamber, and evacuated to 3X 10 -3 Pa. The vacuum chamber is heated to 150 ℃ and kept for 10min, argon is filled, and the flow rate of the argon is 30sccm. Opening a Hall ion source, setting the voltage of the Hall ion source to be 1000v, setting the current to be 0.5A, and treating for 1min to enable the surface tension of the copper foil to reach 65 dynes.
Closing the gate valve until the vacuum degree is 0.4Pa, keeping the argon flow at 30sccm, starting a magnetron sputtering power supply to 80w, taking strontium titanate with the density of 97% as a target material, depositing for 4 minutes, and forming a 150nm strontium titanate film prefabricated layer on the copper foil, wherein the grain size of the strontium titanate film prefabricated layer is 80nm, and the structure is compact.
Closing argon, filling oxygen, ensuring the vacuum degree to be 0.2Pa, setting the heating temperature to 350 ℃, and keeping the temperature for 60min, wherein the oxygen flow is 60 sccm.
Closing an oxygen valve, opening an argon valve, ensuring the vacuum degree to be 0.4Pa, opening a magnetron sputtering power supply, setting the magnetron sputtering current 4A, taking metal copper as a target material, depositing for 10 minutes to form a copper electrode layer, wherein the thickness of the copper electrode layer is 500nm, and the sheet resistance is 0.1 omega/≡to obtain the flexible energy storage film.
Through tests, the thickness of the strontium titanate film in the obtained flexible energy storage film is 120nm, the minimum bending radius of the flexible energy storage film is 3mm, the grain size is 100nm, the dielectric constant is 300, the dielectric loss is 0.008, the breakdown field strength is 1800kV/cm, and the energy storage density is 30J/cm 3 Can be applied to film capacitors.
Example 3:
as shown in FIG. 1, a rolled copper foil having a thickness of 12 μm and a surface roughness of 0.4 μm was used as a substrate, placed in a vacuum chamber, and evacuated to 3X 10 -3 Pa. The vacuum chamber was heated to 150℃for 10min, argon was introduced at a flow rate of 50sccm. Opening a Hall ion source, setting the voltage of the Hall ion source to be 1000v, setting the current to be 0.5A, and treating for 5min to enable the surface tension of the copper foil to reach 60 dyne.
Closing the gate valve until the vacuum degree is 0.2Pa, keeping the argon flow at 50sccm, starting a magnetron sputtering power supply to 120w, taking strontium titanate with the density of 98% as a target material, depositing for 1 minute, and forming a 60nm strontium titanate film prefabricated layer on the copper foil, wherein the grain size of the strontium titanate film prefabricated layer is 120nm, and the structure is compact.
Closing argon, filling oxygen, ensuring the vacuum degree to be 0.6Pa, setting the heating temperature to be 360 ℃, and keeping the temperature for 60min, wherein the oxygen flow is 120 sccm.
Closing an oxygen valve, opening an argon valve, ensuring the vacuum degree to be 0.4Pa, opening a magnetron sputtering power supply, setting the magnetron sputtering current 4A, taking metal copper as a target material, depositing for 10 minutes to form a copper electrode layer, wherein the thickness of the copper electrode layer is 1 mu m, and the sheet resistance is 0.05 omega/≡to obtain the flexible energy storage film.
Through testing, the obtained flexible energy storage film has strontium titanate thinThe thickness of the film is 50nm, the minimum bending radius of the flexible energy storage film is 2.5mm, the grain size is 140nm, the dielectric constant is 310, the dielectric loss is 0.008, the breakdown field strength is 2500kV/cm, and the energy storage density is 40J/cm 3 Can be applied to film capacitors.
Example 4:
as shown in FIG. 1, a rolled copper foil having a thickness of 12 μm and a surface roughness of 0.8 μm was used as a substrate, placed in a vacuum chamber, and evacuated to 3X 10 -3 Pa. The vacuum chamber was heated to 200℃for 10min, argon was introduced at a flow rate of 50sccm. Opening a Hall ion source, setting the voltage of the Hall ion source to be 1000v, setting the current to be 1A, and treating for 5min to enable the surface tension of the copper foil to reach 75 dynes.
Closing the gate valve until the vacuum degree is 0.2Pa, keeping the argon flow at 50sccm, starting a magnetron sputtering power supply to 50w, taking strontium titanate with the density of 96% as a target material, depositing for 2 minutes, and forming a 30nm strontium titanate film prefabricated layer on the copper foil, wherein the grain size of the strontium titanate film prefabricated layer is 10nm, and the structure is compact.
Closing argon, filling oxygen, ensuring the vacuum degree to be 0.6Pa, setting the heating temperature to 400 ℃, and keeping the temperature for 60min, wherein the oxygen flow is 100 sccm.
Closing an oxygen valve, opening an argon valve, ensuring the vacuum degree to be 0.4Pa, opening a magnetron sputtering power supply, setting the magnetron sputtering current 4A, taking metal copper as a target material, depositing for 30 minutes to form a copper electrode layer, wherein the thickness of the copper electrode layer is 2 mu m, and the sheet resistance is 0.002mΩ/≡to obtain the flexible energy storage film.
Through tests, the thickness of the strontium titanate film in the obtained flexible energy storage film is 10nm, the minimum bending radius of the flexible energy storage film is 2mm, the grain size is 30nm, the dielectric constant is 280, the dielectric loss is 0.006, the breakdown field strength is 3000kV/cm, and the energy storage density is 55J/cm 3 Can be applied to film capacitors.
Example 5:
as shown in FIG. 1, an electrolytic copper foil is used as a substrate, the thickness of the copper foil is 18 micrometers, the surface roughness is 0.5 micrometers, and the copper foil is placed in a vacuum chamber and vacuumized to 3X 10 -3 Pa. Vacuum chamberHeating to 250 ℃, keeping the temperature for 10min, and filling argon with the flow of 30sccm. Opening a Hall ion source, setting the voltage of the Hall ion source to be 1000v, setting the current to be 0.5A, and treating for 1min to enable the surface tension of the copper foil to reach 75 dynes.
Closing the gate valve until the vacuum degree is 0.5Pa, keeping the argon flow at 30sccm, starting a magnetron sputtering power supply to 200w, taking strontium titanate with the density of 98% as a target material, depositing for 5 minutes, and forming a 300nm strontium titanate film prefabricated layer on the copper foil, wherein the grain size of the strontium titanate film prefabricated layer is 450nm, and the structure is compact.
Closing argon, filling oxygen with the flow of 70sccm, ensuring the vacuum degree to be 0.3Pa, setting the heating temperature to 600 ℃, and keeping the temperature for 30min.
Closing an oxygen valve, opening an argon valve, ensuring the vacuum degree to be 0.4Pa, opening a magnetron sputtering power supply, setting the magnetron sputtering current 4A, taking metal copper as a target material, depositing for 1 hour to form a copper electrode layer, wherein the thickness of the copper electrode layer is 3 mu m, and the sheet resistance is 0.001mΩ/≡, so that the flexible energy storage film is obtained.
Through tests, the thickness of the strontium titanate film in the obtained flexible energy storage film is 240nm, the minimum bending radius of the flexible energy storage film is 10mm, the grain size is 500nm, the dielectric constant is 300, the dielectric loss is 0.008, the breakdown field strength is 1500kV/cm, and the energy storage density is 25J/cm 3 Can be applied to film capacitors.
Example 6:
as shown in FIG. 1, an electrolytic copper foil is used as a substrate, the thickness of the copper foil is 18 micrometers, the surface roughness is 0.5 micrometers, and the copper foil is placed in a vacuum chamber and vacuumized to 3X 10 -3 Pa. The vacuum chamber is heated to 150 ℃ and kept for 10min, argon is filled, and the flow rate of the argon is 30sccm. Opening a Hall ion source, setting the voltage of the Hall ion source to be 1000v, setting the current to be 0.5A, and treating for 1min to enable the surface tension of the copper foil to reach 65 dynes.
Closing the gate valve until the vacuum degree is 0.4Pa, keeping the argon flow at 30sccm, starting a magnetron sputtering power supply to 200w, taking strontium titanate with the density of 99% as a target material, depositing for 60 minutes, and forming a 3.5-micrometer strontium titanate thin film prefabricated layer on the copper foil, wherein the grain size of the strontium titanate thin film prefabricated layer is 450nm, and the structure is compact.
Closing argon, filling oxygen, ensuring the vacuum degree to be 1Pa, setting the heating temperature to 600 ℃, and keeping the temperature for 30min, wherein the oxygen flow is 150 sccm.
Closing an oxygen valve, opening an argon valve, ensuring the vacuum degree to be 0.4Pa, opening a magnetron sputtering power supply, setting the magnetron sputtering current 4A, taking metal copper as a target material, depositing for 30 minutes to form a copper electrode layer, wherein the thickness of the copper electrode layer is 1.5 mu m, and the sheet resistance is 0.01mΩ/≡to obtain the flexible energy storage film.
Through testing, the thickness of the strontium titanate film in the obtained flexible energy storage film is 3 mu m, the minimum bending radius of the flexible energy storage film is 20mm, the grain size is 500nm, the dielectric constant is 300, the dielectric loss is 0.007, the breakdown field strength is 1000kV/cm, and the energy storage density is 12J/cm 3 Can be applied to film capacitors.
Example 7:
as shown in FIG. 1, an electrolytic copper foil is used as a substrate, the thickness of the copper foil is 12 micrometers, the surface roughness is 0.5 micrometers, and the copper foil is placed in a vacuum chamber and vacuumized to 3X 10 -3 Pa. The vacuum chamber is heated to 150 ℃ and kept for 10min, argon is filled, and the flow rate of the argon is 30sccm. Opening a Hall ion source, setting the voltage of the Hall ion source to be 1000v, setting the current to be 0.5A, and treating for 6min to enable the surface tension of the copper foil to reach 70 dynes.
Closing a gate valve until the vacuum degree is 0.5Pa, keeping the argon flow at 30sccm, starting a magnetron sputtering power supply to 100w, taking strontium titanate with the density of 98% as a target material, depositing for 30 minutes, and forming a 2 mu m strontium titanate film prefabricated layer on the copper foil, wherein the grain size of the strontium titanate film prefabricated layer is 270nm, and the structure is compact.
Closing argon, filling oxygen, ensuring the vacuum degree to be 0.8Pa, setting the heating temperature to 400 ℃, and keeping the temperature for 30min, wherein the oxygen flow is 120 sccm.
Closing an oxygen valve, opening an argon valve, ensuring the vacuum degree to be 0.4Pa, opening a magnetron sputtering power supply, setting the magnetron sputtering current 6A, taking metal copper as a target material, depositing for 10 minutes to form a copper electrode layer, wherein the thickness of the copper electrode layer is 800nm, and the sheet resistance is 0.05 omega/≡to obtain the flexible energy storage film.
Through testing, the thickness of the strontium titanate film in the obtained flexible energy storage film is 1.8 mu m, the minimum bending radius of the flexible energy storage film is 12mm, the grain size is 300nm, the dielectric constant is 310, the dielectric loss is 0.006, the breakdown field strength is 1500kV/cm, and the energy storage density is 25J/cm 3 Can be applied to film capacitors.
Example 8:
as shown in FIG. 1, an electrolytic copper foil is used as a substrate, the thickness of the copper foil is 18 micrometers, the surface roughness is 0.5 micrometers, and the copper foil is placed in a vacuum chamber and vacuumized to 3X 10 -3 Pa. The vacuum chamber is heated to 150 ℃ and kept for 10min, argon is filled, and the flow rate of the argon is 30sccm. Opening a Hall ion source, setting the voltage of the Hall ion source to be 1000v, setting the current to be 0.5A, and treating for 1min to enable the surface tension of the copper foil to reach 60 dyne.
Closing the gate valve until the vacuum degree is 0.1Pa, keeping the argon flow at 30sccm, starting a magnetron sputtering power supply to 90w, taking 97% of strontium titanate with the compactness as a target material, depositing for 40 minutes, and forming a 900nm strontium titanate film prefabricated layer on the copper foil, wherein the grain size of the strontium titanate film prefabricated layer is 160nm, and the structure is compact.
Closing argon, filling oxygen, ensuring the vacuum degree to be 0.5Pa, setting the heating temperature to 300 ℃, and keeping the temperature for 30min, wherein the oxygen flow is 90 sccm.
Closing an oxygen valve, opening an argon valve, ensuring the vacuum degree to be 0.4Pa, opening a magnetron sputtering power supply, setting the magnetron sputtering current 4A, taking metal copper as a target material, depositing for 10 minutes to form a copper electrode layer, wherein the thickness of the copper electrode layer is 100nm, and the sheet resistance is 0.5 omega/≡to obtain the flexible energy storage film.
Through tests, the thickness of the strontium titanate film in the obtained flexible energy storage film is 800nm, the minimum bending radius of the flexible energy storage film is 10mm, the grain size is 200nm, the dielectric constant is 300, the dielectric loss is 0.008, the breakdown field strength is 1300kV/cm, and the energy storage density is 23J/cm 3 Can be applied to film capacitors.
Example 9:
as shown in fig. 1, to electricityThe copper foil is taken as a substrate, the thickness of the copper foil is 12 microns, the surface roughness is 0.8 microns, and the copper foil is placed in a vacuum chamber and vacuumized to 3 multiplied by 10 -3 Pa. The vacuum chamber was heated to 200℃for 10min, argon was introduced at a flow rate of 30sccm. Opening a Hall ion source, setting the voltage of the Hall ion source to be 1000v, setting the current to be 0.5A, and treating for 1min to enable the surface tension of the copper foil to reach 70 dynes.
Closing the gate valve until the vacuum degree is 0.4Pa, keeping the argon flow to be 120sccm, starting a magnetron sputtering power supply to 130w, taking strontium titanate with the density of 98% as a target material, depositing for 20 minutes, forming a 560nm strontium titanate film prefabricated layer on the copper foil, wherein the grain size of the strontium titanate film prefabricated layer is 240nm, and the structure is compact.
Closing argon, filling oxygen, ensuring the vacuum degree to be 0.2Pa, setting the heating temperature to 300 ℃, and keeping the temperature for 30min, wherein the oxygen flow is 50sccm.
Closing an oxygen valve, opening an argon valve, ensuring the vacuum degree to be 0.4Pa, opening a magnetron sputtering power supply, setting the magnetron sputtering current 4A, taking metal copper as a target material, depositing for 10 minutes to form a copper electrode layer, wherein the thickness of the copper electrode layer is 500nm, and the sheet resistance is 0.1 omega/≡to obtain the flexible energy storage film.
Through tests, the thickness of the strontium titanate film in the obtained flexible energy storage film is 500nm, the minimum bending radius of the flexible energy storage film is 6mm, the grain size is 200nm, the dielectric constant is 300, the dielectric loss is 0.006, the breakdown field strength is 1600kV/cm, and the energy storage density is 21J/cm 3 Can be applied to film capacitors.
Example 10:
embodiment 10 differs from embodiment 1 only in that the substrate of embodiment 10 is aluminum foil, resulting in a flexible energy storage film as shown in fig. 2 (f), which can be applied in a film capacitor. Through tests, the thickness of the strontium titanate film in the obtained flexible energy storage film is 120nm, the minimum bending radius of the flexible energy storage film is 5mm, the grain size is 140nm, the dielectric constant is 300, the dielectric loss is 0.009, the breakdown field strength is 1500kV/cm, and the energy storage density is 25J/cm 3 Can be applied to film capacitors.
Comparative example 1:
a strontium titanate energy storage film as shown in fig. 2 (e) was obtained by sequentially forming a strontium titanate film and a Pt electrode layer on a silicon substrate by the magnetron sputtering method of example 1 using a rigid silicon substrate as a substrate.
As can be seen from fig. 2, the strontium titanate ceramic energy storage film of comparative example 1 has no flexibility and has a large grain size. The energy storage film of the embodiment 1 of the invention has flexibility, and the microstructure of the strontium titanate film is compact and uniform, and the grain size is small, so that the bending radius is small and the energy storage density is excellent. While the flexible energy storage film of example 10 was flexible, the grain size was larger, and the bending radius and energy storage performance of the flexible energy storage film were weaker than those of example 1.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (4)

1. The preparation method of the flexible energy storage film is characterized by comprising the following steps:
providing a flexible metal substrate, wherein the flexible metal substrate is used as an electrode, the surface roughness of the flexible metal substrate is 0.4-0.8 mu m, the surface tension of the flexible metal substrate is more than or equal to 60 dynes, and the flexible metal substrate is a rolled copper foil;
taking strontium titanate as a target material, and adopting a magnetron sputtering method to deposit and form a strontium titanate film prefabricated layer on the flexible metal substrate, wherein the power of the magnetron sputtering is 50-200W, the deposition time is 1-60 minutes, the working atmosphere of the magnetron sputtering is argon, the flow of the argon is 30-120 sccm, and the vacuum degree is 0.1-0.5 Pa, and the grain size of the strontium titanate film prefabricated layer is 10-450 nm;
and carrying out heat treatment on the flexible metal substrate with the strontium titanate film prefabricated layer to obtain a strontium titanate layer, thereby obtaining the flexible energy storage film, wherein the grain size of the strontium titanate layer is 30-500 nm, the heat treatment temperature is 300-600 ℃ and the heat treatment time is 20-60 minutes.
2. The method for preparing a flexible energy storage film according to claim 1, wherein the thickness of the strontium titanate thin film preformed layer is 30 nm-3 μm.
3. The method for producing a flexible energy storage film according to claim 1, wherein oxygen is supplied during the heat treatment, the flow rate of the oxygen is 30sccm to 150sccm, and the vacuum degree is 0.1Pa to 1Pa.
4. The method for producing a flexible energy storage film according to claim 1, wherein the thickness of the flexible metal substrate is 12 μm to 18 μm.
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