CN110767447B - Flexible energy storage film, preparation method thereof and film capacitor - Google Patents
Flexible energy storage film, preparation method thereof and film capacitor Download PDFInfo
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- CN110767447B CN110767447B CN201810829735.3A CN201810829735A CN110767447B CN 110767447 B CN110767447 B CN 110767447B CN 201810829735 A CN201810829735 A CN 201810829735A CN 110767447 B CN110767447 B CN 110767447B
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- 238000004146 energy storage Methods 0.000 title claims abstract description 140
- 239000003990 capacitor Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 216
- 229910052751 metal Inorganic materials 0.000 claims abstract description 108
- 239000002184 metal Substances 0.000 claims abstract description 108
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 107
- 239000000758 substrate Substances 0.000 claims abstract description 88
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000001914 filtration Methods 0.000 claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 238000007733 ion plating Methods 0.000 claims abstract description 36
- 229910052786 argon Inorganic materials 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000000151 deposition Methods 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- 239000013077 target material Substances 0.000 claims abstract description 17
- 239000010408 film Substances 0.000 claims description 127
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 65
- 239000011889 copper foil Substances 0.000 claims description 58
- 230000015556 catabolic process Effects 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
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- 230000008021 deposition Effects 0.000 claims description 15
- 230000003746 surface roughness Effects 0.000 claims description 15
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- 239000010409 thin film Substances 0.000 claims description 13
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- 238000000605 extraction Methods 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000003989 dielectric material Substances 0.000 abstract description 3
- 238000005452 bending Methods 0.000 description 27
- 150000002500 ions Chemical class 0.000 description 20
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- 239000000919 ceramic Substances 0.000 description 11
- 238000001755 magnetron sputter deposition Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 238000007254 oxidation reaction Methods 0.000 description 3
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- 238000003980 solgel method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
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- 239000000788 chromium alloy Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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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
-
- 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
- C23C14/083—Oxides of refractory metals or yttrium
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- 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
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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
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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
- H01G4/005—Electrodes
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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
- H01G4/33—Thin- or thick-film capacitors
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Abstract
The invention relates to a flexible energy storage film, a preparation method thereof and a film capacitor. The preparation method comprises the following steps: providing a flexible metal substrate; depositing a titanium dioxide prefabricated layer on the flexible metal substrate by using titanium as a target material and adopting a magnetic filtration multi-arc ion plating method, wherein the working atmosphere in the magnetic filtration multi-arc ion plating method is a mixed gas of argon and oxygen; and carrying out heat treatment on the flexible metal substrate deposited with the titanium dioxide prefabricated layer to obtain the flexible energy storage film. The flexible energy storage film comprises a flexible metal substrate and a titanium dioxide layer formed on the flexible metal substrate. The preparation method not only realizes the flexibility of the energy storage film, but also 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.
Description
Technical Field
The invention relates to the field of energy sources, in particular to a flexible energy storage film, a preparation method thereof and a film capacitor.
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 the above, it is necessary to provide a flexible energy storage thin film, a preparation method thereof, and a thin film capacitor for solving the problem of insufficient flexibility of the ceramic energy storage thin 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 preparation method of a flexible energy storage thin film comprises the following steps:
providing a flexible metal substrate;
depositing a titanium dioxide prefabricated layer on the flexible metal substrate by using titanium as a target material and adopting a magnetic filtration multi-arc ion plating method, wherein the working atmosphere in the magnetic filtration multi-arc ion plating method is a mixed gas of argon and oxygen;
and carrying out heat treatment on the flexible metal substrate deposited with the titanium dioxide prefabricated layer to obtain the flexible energy storage film.
In one embodiment, 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 1 minute-80 minutes.
In one embodiment, the flow rate of the mixed gas is 20sccm to 50sccm, the flow rate ratio of argon to oxygen in the mixed gas is 9:1 to 1:1, and the vacuum degree is 2.0 × 10-2Pa～6.0×10-2Pa。
In one embodiment, the thickness of the titanium dioxide prefabricated layer is 40 nm-3.2 μm, and the grain size of the titanium dioxide prefabricated layer is 20 nm-200 nm.
In one embodiment, oxygen is introduced during the heat treatment, the flow rate of the oxygen is 100sccm to 200sccm, and the vacuum degree is 0.1Pa to 1 Pa.
In one embodiment, the temperature of the heat treatment is 300-500 ℃ and the time is 30-300 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 μm; and/or
The surface tension of the flexible metal substrate is more than or equal to 60 dynes; and/or
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.
According to the invention, the flexible metal substrate is adopted, and the titanium dioxide layer is deposited on the flexible metal substrate by a magnetic filtration multi-arc ion plating method to form the flexible energy storage film, so that the flexibility of the ceramic energy storage film is realized. And the bonding force between the titanium dioxide layer and the flexible metal substrate and the film quality are improved by controlling the arc current, the extraction current, the bias voltage of the flexible metal substrate, the working atmosphere and the like of the magnetic filtration multi-arc ion plating, and the oxygen vacancy and the residual stress are eliminated by heat treatment to obtain the titanium dioxide layer with compact structure and uniform grain distribution, thereby obtaining the flexible energy storage film with high energy storage density and high bending property. After the flexible energy storage film is bent for multiple times, the retention rate of the energy storage density and the stability of the binding force are good, and the reliability is high.
The flexible energy storage film obtained by the preparation method comprises a flexible metal substrate and a titanium dioxide layer formed on the flexible metal substrate.
In one embodiment, the thickness of the titanium dioxide layer is 30nm to 2 μm, and the grain size of the titanium dioxide layer is 30nm to 300 nm.
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 μm; and/or
The surface tension of the flexible metal substrate is more than or equal to 60 dynes; and/or
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 mm-20 mm; and/or
The breakdown field strength of the flexible energy storage film is 1800 kV/cm-3500 kV/cm; and/or
The energy storage density of the flexible energy storage film is 20J/cm3～60J/cm3(ii) a And/or
The adhesion force of the titanium dioxide layer and the flexible metal substrate 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.
A film capacitor, the film capacitor includes as above-mentioned 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.
Drawings
FIG. 1 is a schematic structural diagram of a flexible energy storage film according to the present invention;
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 titanium dioxide layer.
Detailed Description
The flexible energy storage film, the preparation method thereof and the film capacitor provided by the invention are further described below.
The preparation method of the flexible energy storage film provided by the invention comprises the following steps:
s1, providing a flexible metal substrate;
s2, depositing a titanium dioxide prefabricated layer on the flexible metal substrate by using titanium as a target material and adopting a magnetic filtration multi-arc ion plating method, wherein the working atmosphere in the magnetic filtration multi-arc ion plating method is a mixed gas of argon and oxygen;
and S3, performing heat treatment on the flexible metal substrate deposited with the titanium dioxide prefabricated layer to obtain the flexible energy storage film.
In step S1, the flexible metal substrate is not limited as long as it has good flexibility, strong high-temperature oxidation resistance, conductivity, and no reaction with the titanium dioxide 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.
Taking into account copperThe foil is the most cost-effective metal material in the field of electronics, and has a resistivity of 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 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 is, the better the flexibility is, and therefore, the thickness of the flexible metal substrate is 12 to 18 μm, and more preferably, a rolled copper foil of 12 μm.
In the film capacitor, the flexible metal substrate is used as an electrode, the actual contact area of the titanium dioxide layer and the electrode is related to the surface roughness of the flexible metal 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 metal substrate is too large, which easily causes holes on the surface of the titanium dioxide layer, and affects the energy storage performance of the flexible energy storage film. Therefore, the surface roughness of the flexible metal substrate is 0.4 μm to 0.8 μm.
The surface tension of the flexible metal substrate is more than or equal to 60 dynes, preferably more than 60 dynes, and the higher the surface tension of the flexible metal substrate is, the stronger the binding force between the titanium dioxide layer and the flexible metal substrate is.
The surface activity can be increased by treating the surface of the flexible metal substrate, thereby increasing the surface tension. Preferably, the treatment method comprises the following steps: the flexible metal substrate is heated at a set temperature of 100-300 ℃ for 10-30 minutes, and then is processed by a Hall ion source with a voltage of 800-2000V and a current of 0.5-2A for 1-10 minutes.
In dielectric materials, the energy storage density is related to the dielectric constant and breakdown field strength of the material, while in paraelectric materials, the energy storage density can be calculated by the following formula:
wherein epsilon0Is a vacuum dielectric constant (8.854X 10)-12F/m)，εrIs a relative dielectric constant, EbIs the breakdown field strength. Therefore, a high breakdown field strength is more favorable for improving the energy storage density.
The titanium dioxide ceramic has higher breakdown field strength (more than 1000kV/cm), and although the dielectric constant is only about 120, the energy storage density can reach 15J/cm3. If the titanium dioxide ceramic is made into a film, the energy storage density is further improved. However, the energy of particles in the conventional magnetron sputtering, sol-gel process and other deposition processes is low, the binding force between the titanium dioxide layer and the flexible metal substrate is poor, and the high-reliability energy storage ceramic film cannot be prepared on the flexible metal substrate. Therefore, in step S2, the present invention deposits a titanium dioxide layer on the flexible metal substrate by using a magnetic filtering multi-arc ion plating method.
As shown in FIG. 2, the magnetic filtration multi-arc ion plating device of the invention comprises a vacuum arc source 1, a lighting device 2, a visible window 3, a filtration magnetic field 4, a focusing magnetic field 5 and 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 titanium metal target 11, the titanium metal 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 to pass through a filtration magnetic field 4, the charged particles move along magnetic lines of force, and the uncharged metal liquid drops 13 are filtered by the filtration magnetic field 4. 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, strong electric potential is formed between the electron cloud and the ions 14 after the electron cloud is separated from the ions 14, the ions 14 are led out and deposited on the flexible metal substrate 10 together with the electrons 12, the magnetic filtration multi-arc ion plating process is completed, and a titanium dioxide prefabricated layer 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 generate metal atoms 15, so that the surface of the flexible metal substrate 10 is cleaned and activated, the surface activity of the flexible metal substrate 10 is enhanced, and the bonding force between the flexible metal substrate and a titanium dioxide prefabricated layer obtained through deposition 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 titanium dioxide prefabricated layer formed by the magnetic filtration multi-arc ion plating method is higher by one order of magnitude than that of the titanium dioxide layer formed by the magnetron sputtering method and the like, and further, the titanium dioxide prefabricated layer formed by the magnetic filtration multi-arc ion plating method has higher binding force with the flexible metal substrate, and the reliability of the flexible energy storage film is high.
Preferably, the flow rate of the mixed gas is 20sccm to 50sccm, the flow rate ratio of argon to oxygen in the mixed gas is 9:1 to 1:1, and the vacuum degree is 2.0 × 10-2Pa～6.0×10-2Pa. In the magnetic filtering multi-arc ion plating method, the argon is easier to start arc, and Ar in the chamber+The more molecules, the larger kinetic energy is generated, which is more beneficial to the target ion escape. The oxygen is used as a reaction gas, the titanium metal target material is unstable in operation due to too high concentration, but the titanium metal target material is not favorable for forming a titanium dioxide prefabricated layer due to too low concentration.
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 1 min-80 min. Wherein the deposition time and the deposition rate determine the deposition thickness of the titanium dioxide preform layer, and the deposition rate can be determined according to the arc current, the extraction current and the bias voltage applied to the flexible metal substrate.
Considering that the thickness of the titanium dioxide layer affects the breakdown field strength and the bending radius, the thinner the thickness is, the larger the breakdown field strength is, and the smaller the minimum bending radius is. However, if the thickness of the titanium oxide layer is thinner than the electron tunneling thickness, the loss increases exponentially, and meanwhile, if the thickness of the titanium oxide layer is thinner than the roughness of the flexible metal substrate, pinholes are easily generated on the surface thereof, resulting in various degradation of electrical properties. Therefore, the thickness of the titanium dioxide prefabricated layer obtained by deposition is preferably 40 nm-3.2 μm, and the grain size of the titanium dioxide prefabricated layer is 20 nm-200 nm.
If the titanium metal target material has low density, the surface and the inner air holes of the titanium metal target material are more, and the titanium metal target material is easy to generate microcracks under the action of high pressure and high temperature during magnetron sputtering, and the microcracks are expanded to cause the titanium metal target material to crack. Therefore, the compactness of the titanium 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 step S3, the flexible metal substrate deposited with the titanium dioxide pre-fabricated layer is subjected to a heat treatment at a temperature of 300 to 500 ℃ for 30 to 300 minutes. The heat treatment is carried out for 30 to 300 minutes at the temperature of between 300 and 500 ℃, so that a large amount of non-equilibrium defects such as lattice mismatch, lattice reconstruction, impurities, phase change and the like in the titanium dioxide prefabricated layer can disappear, and the titanium dioxide layer is obtained. Compared with the titanium dioxide prefabricated layer, the internal stress of the titanium dioxide layer is obviously reduced.
Preferably, oxygen is introduced during the heat treatment, the flow rate of the oxygen is 100sccm to 200sccm, and the vacuum degree is 0.1Pa to 1 Pa. Oxygen can eliminate oxygen vacancy of the titanium dioxide prefabricated layer in the deposition process, defects of the titanium dioxide layer can be further reduced, breakdown field strength and energy storage density are improved, residual stress can be eliminated, flexibility of the film is improved, and bending resistance is improved.
According to the invention, the flexible metal substrate is adopted, and the titanium dioxide layer is deposited on the flexible metal substrate by a magnetic filtration multi-arc ion plating method to form the flexible energy storage film, so that the flexibility of the ceramic energy storage film is realized. And the bonding force between the titanium dioxide layer and the flexible metal substrate and the film quality are improved by controlling the arc current, the extraction current, the bias voltage of the flexible metal substrate, the working atmosphere and the like of the magnetic filtration multi-arc ion plating, and the oxygen vacancy and the residual stress are eliminated by heat treatment to obtain the titanium dioxide layer with compact structure and uniform grain distribution, thereby obtaining the flexible energy storage film with high energy storage density and high bending property. After the flexible energy storage film is bent for multiple times, the retention rate of the energy storage density and the stability of the binding force are good, and the reliability is high.
As shown in fig. 1, the invention further provides a flexible energy storage thin film obtained by the preparation method, wherein the flexible energy storage thin film comprises a flexible metal substrate 10 and a titanium dioxide layer 20 formed on the flexible metal substrate 10.
Preferably, the thickness of the titanium dioxide layer 20 is 30nm to 2 μm, and the crystal grain size of the titanium dioxide layer 20 is 30nm to 300 nm.
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 2-20 mm; and/or
The breakdown field strength of the flexible energy storage film is 1800 kV/cm-3500 kV/cm; and/or
The energy storage density of the flexible energy storage film is 20J/cm3～60J/cm3(ii) a And/or
The adhesion between the titanium dioxide layer 20 and the flexible metal substrate 10 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, the preparation method thereof, and the film capacitor will be further described by the following specific examples.
Example 1:
using flexible electrolytic copper foil as substrate, the thickness is 18 μm, the surface roughness is 0.8 μm, placing in vacuum cavity, vacuumizing to 3 × 10-3Pa. Heating the vacuum chamber to 150 deg.C, holding for 10min, introducing argon gas at flow rate of 20sccm and vacuum degree of 2 × 10-2And Pa, 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.
The vacuum degree is maintained at 2.0X 10-2Pa, argon flow of 18sccm, oxygen gas of 2sccm, magnetic filtration multi-arc ion plating power supply, arc current of 50A, current of 9A, bias voltage of 5V applied to the flexible electrolytic copper foil, titanium metal as a target material, deposition time of 1min, and formation of a titanium dioxide layer with a thickness of 40nm on the copper foil, wherein the grain size is 20 nm.
And (3) closing a magnetic filtration multi-arc ion plating power supply, closing argon, opening the flow of large oxygen to 100sccm, keeping the vacuum degree of the vacuum cavity at 0.1Pa, heating the temperature at 300 ℃, keeping the temperature for 30min, and eliminating oxygen vacancies and residual stress of the titanium dioxide prefabricated layer to obtain the flexible energy storage film. The obtained flexible energy storage film comprises a flexible electrolytic copper foil and a titanium dioxide layer formed on the flexible electrolytic copper foil.
And depositing copper metal on the titanium dioxide layer of the flexible energy storage film by a magnetron sputtering process to be used as an upper electrode, and carrying out electrical property test.
Tests prove that the thickness of a titanium dioxide layer in the obtained flexible energy storage film is 30nm, the grain size is 30nm, the bonding force between the titanium dioxide layer and the electrolytic copper foil is 5B, the minimum bending radius of the flexible energy storage film is 6mm, the breakdown field strength is 2000kV/cm, and the energy storage density is 35J/cm3. After 1000 times of bending, the binding force of the titanium dioxide layer and the electrolytic copper foil is 5B, and the energy storage density is 34.8J/cm3The retention rate is 99.5%, and the film capacitor can be applied to film capacitors.
Example 2:
using flexible silver foil as substrate, the thickness of the silver foil is 12 μm, the surface roughness is 0.5 μm, placing in vacuum cavity, and vacuumizing to 3 × 10-3Pa. Heating the vacuum chamber to 100 deg.C, maintaining for 20min, introducing argon gas with flow rate of 30sccm and vacuum degree of 3 × 10-2And Pa, opening the Hall ion source, setting the voltage of the Hall ion source to be 800V and the current to be 0.6A, and treating for 5min to enable the surface tension of the copper foil to reach 65 dynes.
The vacuum degree is maintained at 3.0X 10-2Pa, the flow of argon gas is 25sccm, oxygen is opened to enable the flow of oxygen to be 5sccm, a magnetic filtration multi-arc ion plating power supply is opened, the arc current is adjusted to 55A, the current is led out to be 10A, the bias voltage applied to the flexible silver foil is 6V, titanium metal is used as a target material, the deposition time is 10min, a titanium dioxide layer with the thickness of 400nm is formed on the copper foil, and the grain size is 80 nm.
And (3) closing a magnetic filtration multi-arc ion plating power supply, closing argon, opening the flow of large oxygen to 150sccm, keeping the vacuum degree of the vacuum cavity at 0.5Pa, heating the temperature to 400 ℃, keeping the temperature for 3h, eliminating oxygen vacancies and residual stress of the titanium dioxide prefabricated layer, and obtaining the flexible energy storage film. The obtained flexible energy storage film comprises a flexible silver foil and a titanium dioxide layer formed on the flexible silver foil.
And depositing copper metal on the titanium dioxide layer of the flexible energy storage film by a magnetron sputtering process to be used as an upper electrode, and carrying out electrical property test.
Tests prove that the thickness of a titanium dioxide layer in the obtained flexible energy storage film is 300nm, the grain size is 120nm, the bonding force between the titanium dioxide layer and the flexible silver foil is 5B, the minimum bending radius of the flexible energy storage film is 5mm, the breakdown field strength is 2400kV/cm, and the energy storage density is 40J/cm3. After 1000 times of bending, the binding force of the titanium dioxide layer and the flexible silver foil is 5B, and the energy storage density is 39.8J/cm3The retention rate is 99.6%, and the film capacitor can be applied to film capacitors.
Example 3:
using flexible rolled copper foil as substrate, the copper foil thickness is 12 μm, the surface roughness is 0.4 μm, placing in vacuum cavity, vacuumizing to 3 × 10-3Pa. Heating the vacuum chamber to 300 deg.C, maintaining for 30min, introducing argon gas with flow rate of 50sccm and vacuum degree of 6 × 10-2And Pa, opening the Hall ion source, setting the voltage of the Hall ion source to be 1500V and the current to be 2A, and treating for 10min to enable the surface tension of the copper foil to reach 75 dynes.
The vacuum degree is maintained at 2.0X 10-2Pa, argon flow of 15sccm, oxygen of 5sccm, magnetic filtration multi-arc ion plating power supply, arc current of 60A, current of 11A, bias voltage of 10V applied to the flexible rolled copper foil, titanium metal as a target material, deposition time of 1.5min, and formation of a titanium dioxide layer with a thickness of 80nm on the copper foil, wherein the grain size is 20 nm.
And (3) closing a magnetic filtration multi-arc ion plating power supply, closing argon, opening the flow of large oxygen to 200sccm, keeping the vacuum degree of the vacuum cavity at 1Pa, heating the temperature at 300 ℃, keeping the temperature for 5h, eliminating oxygen vacancies and residual stress of the titanium dioxide prefabricated layer, and obtaining the flexible energy storage film. The obtained flexible energy storage film comprises a flexible rolled copper foil and a titanium dioxide layer formed on the flexible rolled copper foil.
And depositing copper metal on the titanium dioxide layer of the flexible energy storage film by a magnetron sputtering process to be used as an upper electrode, and carrying out electrical property test.
Through testing, the obtained flexible energy storageThe thickness of a titanium dioxide layer in the film is 50nm, the grain size is 30nm, the binding force between the titanium dioxide layer and the rolled copper foil is 5B, the minimum bending radius of the flexible energy storage film is 2mm, the breakdown field strength is 3500kV/cm, and the energy storage density is 60J/cm3. After 1000 times of bending, the binding force of the titanium dioxide layer and the rolled copper foil is 5B, and the energy storage density is 59.9J/cm3The retention rate is 99.8%, and the film capacitor 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 cavity, and vacuumizing to 3 × 10-3Pa. Heating the vacuum chamber to 100 deg.C, maintaining for 20min, introducing argon gas at a flow rate of 30sccm and a vacuum degree of 4 × 10-2And Pa, opening the Hall ion source, setting the voltage of the Hall ion source to be 2000V and the current to be 2A, and treating for 10min to enable the surface tension of the copper foil to reach 70 dynes.
The vacuum degree is kept at 6.0X 10-2Pa, the flow of argon gas is 25sccm, oxygen is opened to enable the flow of oxygen to be 25sccm, a magnetic filtration multi-arc ion plating power supply is opened, the arc current is adjusted to 45A, the current is led out to be 7A, the bias voltage applied to the flexible gold foil is 10V, titanium metal is used as a target material, the deposition time is 80min, and a titanium dioxide layer with the thickness of 3.2 mu m is formed on the copper foil, wherein the grain size is 200 nm.
And (3) closing a magnetic filtration multi-arc ion plating power supply, closing argon, opening the flow of large oxygen to 150sccm, keeping the vacuum degree of the vacuum cavity at 0.5Pa, heating the temperature to 500 ℃, keeping the temperature for 3h, eliminating oxygen vacancies and residual stress of the titanium dioxide prefabricated layer, and obtaining the flexible energy storage film. The obtained flexible energy storage film comprises a flexible gold foil and a titanium dioxide layer formed on the flexible gold foil.
And depositing copper metal on the titanium dioxide layer of the flexible energy storage film by a magnetron sputtering process to be used as an upper electrode, and carrying out electrical property test.
Tests prove that the thickness of a titanium dioxide layer in the obtained flexible energy storage film is 2 mu m, the grain size is 300nm, the bonding force between the titanium dioxide layer and the flexible gold foil is 5B, and the minimum bending radius of the flexible energy storage film is20mm, breakdown field strength of 1800kV/cm and energy storage density of 20J/cm3. After 1000 times of bending, the binding force of the titanium dioxide layer and the flexible gold foil is 5B, and the energy storage density is 19.9J/cm3The retention rate is 99.5%, and the film capacitor can be applied to film capacitors.
Example 5:
using flexible platinum as substrate, the thickness of platinum is 12 μm, the surface roughness is 0.6 μm, placing in vacuum cavity, and vacuumizing to 3 × 10-3Pa. Heating the vacuum chamber to 200 deg.C, maintaining for 25min, introducing argon gas with flow rate of 40sccm and vacuum degree of 5 × 10-2And Pa, opening the Hall ion source, setting the voltage of the Hall ion source to be 1200V and the current to be 1.2A, and treating for 6min to enable the surface tension of the copper foil to reach 65 dynes.
The vacuum degree is maintained at 4.0X 10-2Pa, the flow of argon gas is 35sccm, oxygen is opened to enable the flow of oxygen to be 5sccm, a magnetic filtration multi-arc ion plating power supply is opened, the arc current is adjusted to 55A, the current is led out to 10A, the bias voltage applied to the flexible platinum is 7V, titanium metal is used as a target material, the deposition time is 50min, a titanium dioxide layer with the thickness of 200nm is formed on the copper foil, and the grain size is 100 nm.
And (3) closing a magnetic filtration multi-arc ion plating power supply, closing argon, opening the flow of large oxygen to 160sccm, keeping the vacuum degree of the vacuum cavity at 0.6Pa, heating the temperature at 350 ℃, keeping the temperature for 2h, eliminating oxygen vacancies and residual stress of the titanium dioxide prefabricated layer, and obtaining the flexible energy storage film. The obtained flexible energy storage film comprises flexible platinum and a titanium dioxide layer formed on the flexible platinum.
And depositing copper metal on the titanium dioxide layer of the flexible energy storage film by a magnetron sputtering process to be used as an upper electrode, and carrying out electrical property test.
Tests prove that the thickness of a titanium dioxide layer in the obtained flexible energy storage film is 150nm, the grain size is 180nm, the bonding force between the titanium dioxide layer and flexible platinum is 5B, the minimum bending radius of the flexible energy storage film is 10mm, the breakdown field strength is 1900kV/cm, and the energy storage density is 28J/cm3. After 1000 times of bending, the binding force between the titanium dioxide layer and the flexible platinum is 5B, and the energy storage density is 27.9J/cm3The retention rate is 99.6%, and the film capacitor can be applied to film capacitors.
Example 6
Using flexible rolled copper foil as substrate, the thickness is 18 μm, the surface roughness is 0.8 μm, placing in vacuum cavity, vacuumizing to 3 × 10-3Pa. Heating the vacuum chamber to 150 deg.C, holding for 10min, introducing argon gas at flow rate of 20sccm and vacuum degree of 2 × 10-2And Pa, 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.
The vacuum degree is maintained at 2.0X 10-2Pa, argon flow of 18sccm, oxygen of 2sccm, magnetic filtration multi-arc ion plating power supply, arc current of 50A, current of 9A, bias voltage of 5V applied to the flexible rolled copper foil, titanium metal as a target material, deposition time of 1min, and formation of a titanium dioxide layer with a thickness of 40nm on the copper foil, wherein the grain size is 20 nm.
And (3) closing a magnetic filtration multi-arc ion plating power supply, closing argon, opening the flow of large oxygen to 100sccm, keeping the vacuum degree of the vacuum cavity at 0.1Pa, heating the temperature at 300 ℃, keeping the temperature for 30min, and eliminating oxygen vacancies and residual stress of the titanium dioxide prefabricated layer to obtain the flexible energy storage film. The obtained flexible energy storage film comprises a flexible rolled copper foil and a titanium dioxide layer formed on the flexible rolled copper foil.
And depositing copper metal on the titanium dioxide layer of the flexible energy storage film by a magnetron sputtering process to be used as an upper electrode, and carrying out electrical property test.
Tests prove that the thickness of a titanium dioxide layer in the obtained flexible energy storage film is 30nm, the grain size is 30nm, the bonding force between the titanium dioxide layer and the electrolytic copper foil is 5B, the minimum bending radius of the flexible energy storage film is 3mm, the breakdown field strength is 2000kV/cm, and the energy storage density is 35J/cm3. After 1000 times of bending, the binding force of the titanium dioxide layer and the electrolytic copper foil is 5B, and the energy storage density is 34.8J/cm3The retention rate is 99.5%, and the film capacitor can be applied to film capacitors.
Comparative example 1:
comparative example 1 differs from example 1 only in that a titanium dioxide preform layer was deposited on a flexible electrolytic copper foil using a magnetron sputtering method.
Tests prove that the thickness of a titanium dioxide layer in the obtained flexible energy storage film is 30nm, the grain size is 30nm, the bonding force between the titanium dioxide layer and the electrolytic copper foil is 4B, the minimum bending radius of the flexible energy storage film is 10mm, the breakdown field strength is 2000kV/cm, and the energy storage density is 35J/cm3. After 1000 times of bending, the binding force of the titanium dioxide layer and the electrolytic copper foil is 3B, and the energy storage density is 21J/cm3The retention ratio was 60%.
Comparative example 2:
comparative example 1 differs from example 1 only in that a prefabricated layer of titanium dioxide is deposited on a flexible electrolytic copper foil using a sol-gel process.
Tests prove that the thickness of a titanium dioxide layer in the obtained flexible energy storage film is 30nm, the grain size is 30nm, the bonding force between the titanium dioxide layer and the electrolytic copper foil is 3B, the minimum bending radius of the flexible energy storage film is 13mm, the breakdown field strength is 1800kV/cm, and the energy storage density is 30J/cm3. After 1000 times of bending, the binding force of the titanium dioxide layer and the electrolytic copper foil is 2B, and the energy storage density is 15J/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 (11)
1. A preparation method of a flexible energy storage film is characterized by comprising the following steps:
providing a flexible metal substrate;
titanium metal is used as a target material, a titanium dioxide prefabricated layer is deposited on the flexible metal substrate by adopting a magnetic filtration multi-arc ion plating method, wherein the working atmosphere in the magnetic filtration multi-arc ion plating method is a mixed gas of argon and oxygen, 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 1 minute-80 minutes;
and carrying out heat treatment on the flexible metal substrate deposited with the titanium dioxide prefabricated layer to obtain the flexible energy storage film.
2. The method for preparing the flexible energy storage thin film according to claim 1, wherein the flow rate of the mixed gas is 20sccm to 50sccm, the flow rate ratio of argon to oxygen in the mixed gas is 9:1 to 1:1, and the vacuum degree is 2.0 x 10-2Pa～6.0×10-2Pa。
3. The method for preparing the flexible energy storage film as claimed in claim 1, wherein the thickness of the titanium dioxide prefabricated layer is 40nm to 3.2 μm, and the grain size of the titanium dioxide prefabricated layer is 20nm to 200 nm.
4. The method for preparing the flexible energy storage film according to claim 1, wherein oxygen is filled during the heat treatment, the flow rate of the oxygen is 100sccm to 200sccm, and the vacuum degree is 0.1Pa to 1 Pa.
5. The method for preparing the flexible energy storage film according to claim 1, wherein the temperature of the heat treatment is 300-500 ℃ and the time is 30-300 minutes.
6. The method for preparing the flexible energy storage film according to claim 1, wherein the thickness of the flexible metal substrate is 12 μm to 18 μm; and/or
The surface roughness of the flexible metal substrate is 0.4-0.8 μm; and/or
The surface tension of the flexible metal substrate is more than or equal to 60 dynes; and/or
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.
7. A flexible energy storage thin film obtained by the preparation method according to any one of claims 1 to 6, wherein the flexible energy storage thin film comprises a flexible metal substrate and a titanium dioxide layer formed on the flexible metal substrate.
8. The flexible energy storage film of claim 7, wherein the thickness of the titanium dioxide layer is 30nm to 2 μm, and the grain size of the titanium dioxide layer is 30nm to 300 nm.
9. The flexible energy storage film of claim 7, wherein the flexible metal substrate has a thickness of 12 μm to 18 μm; and/or
The surface roughness of the flexible metal substrate is 0.4-0.8 μm; and/or
The surface tension of the flexible metal substrate is more than or equal to 60 dynes; and/or
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.
10. The flexible energy storage film of claim 7, wherein the flexible energy storage film has a minimum bend radius of 2mm to 20 mm; and/or
The breakdown field strength of the flexible energy storage film is 1800 kV/cm-3500 kV/cm; and/or
The energy storage density of the flexible energy storage film is 20J/cm3～60J/cm3(ii) a And/or
The adhesion force of the titanium dioxide layer and the flexible metal substrate is 5B.
11. A film capacitor, characterized in that it comprises a flexible energy storing film according to any of claims 7 to 10.
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