WO2018177019A1 - 用于高密度储能的铁酸铋基电介质薄膜及其制备方法和应用 - Google Patents

用于高密度储能的铁酸铋基电介质薄膜及其制备方法和应用 Download PDF

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WO2018177019A1
WO2018177019A1 PCT/CN2018/074659 CN2018074659W WO2018177019A1 WO 2018177019 A1 WO2018177019 A1 WO 2018177019A1 CN 2018074659 W CN2018074659 W CN 2018074659W WO 2018177019 A1 WO2018177019 A1 WO 2018177019A1
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barium ferrite
energy storage
dielectric film
based ceramic
barium
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French (fr)
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林元华
潘豪
南策文
沈洋
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清华大学
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Definitions

  • the invention belongs to the field of dielectric materials, in particular, the invention relates to a barium ferrite-based dielectric film for high-density energy storage, a preparation method and application thereof.
  • dielectric capacitors are widely used in electronic circuits due to their fast charge and discharge speed and ultra-high power density. They can realize DC-blocking, coupling, bypass, filtering, tuning loop and energy conversion. And other functions.
  • its lower energy storage density has become a bottleneck for its further development and application.
  • Commercially available dielectric materials currently have a storage density of only about 2 J/cm 3 , which is one to two orders of magnitude lower than electrochemical capacitors or batteries. Therefore, exploring dielectric materials with high energy storage density has been a hot topic in this field.
  • the ceramic thin film dielectric has a large dielectric constant and a high breakdown field strength, and is the most promising dielectric material system for obtaining high energy storage density. At the same time, due to its small size, good mechanical properties and excellent high temperature resistance, it is expected to be small in devices. Application, integration, and extreme conditions. High energy storage densities of 30 to 60 J/cm 3 have been achieved in a large class of lead zirconate titanate (PZT) based thin film dielectrics. Representative examples such as: Zhongqiang Hu and other Pb 0.96 La 0.04 Zr 0.98 Ti 0.02 O 3 antiferroelectric film prepared by chemical deposition have a storage density of 61 J/cm 3 and maintain performance from room temperature to 225 ° C.
  • an object of the present invention is to provide a barium ferrite-based dielectric film for high-density energy storage and a preparation method and application thereof.
  • the dielectric film has excellent energy storage performance, a storage density of 70.3 J/cm 3 and a high energy storage efficiency of 70%.
  • the present invention provides a barium ferrite-based dielectric film for high density energy storage.
  • the chemical composition of the dielectric film is of the formula (1-x)BiFeO 3 -xSrTiO 3 , wherein x is a mole fraction and 0 ⁇ x ⁇ 1.
  • bismuth ferrite (BiFeO 3 ) is a kind of multi-iron material, which has ferroelectricity and antiferromagneticity, accompanied by weak ferromagnetism, and its ferroelectricity is caused by the fact that Bi ions have lone pair electrons.
  • its iron electrodeposition is higher than 100uC/cm 2 , but it is difficult to prepare pure barium ferrite, in which there are secondary phases and various defects, which makes it difficult to measure its true iron polarization, usually in iron.
  • the iron electrodeposition measured in the acid strontium ceramic is only a few uC/cm 2 ;
  • the barium titanate (SrTiO 3 ) has a typical perovskite structure and is a widely used electronic functional ceramic material with a high dielectric constant. It has the advantages of low dielectric loss and good thermal stability, and is widely used in the electronics, machinery and ceramic industries.
  • the two are formed into a solid solution (1-x)BiFeO 3 -xSrTiO 3 (x is a mole fraction, 0 ⁇ x ⁇ 1), and by obtaining the value of x, the obtained dielectric film has excellent ferroelectric properties and insulation.
  • the property has a breakdown field strength of 3 to 4.5 MV/cm, a storage density of up to 70.3 J/cm 3 , and a high energy storage efficiency of 70%.
  • this barium ferrite-based dielectric film has a large dielectric constant, small dielectric loss, high breakdown field strength and excellent energy storage performance, and is a promising application for embedded capacitors. Materials in the fields of electrostatic energy storage components, pulse power technology, etc.
  • barium ferrite-based dielectric film for high-density energy storage may further have the following additional features:
  • the barium ferrite-based dielectric film for high density energy storage has a thickness of from 150 nm to 2 ⁇ m. Thereby, it is advantageous to improve the growth quality of the dielectric film and improve the energy storage performance of the dielectric film.
  • the barium ferrite-based dielectric film for high density energy storage is doped with a transition element at the Fe site.
  • the insulating property of the film can be improved, and the energy storage performance of the dielectric film can be further improved.
  • the transition element has a doping amount of from 0.1% by weight to 2.0% by weight. Thereby, the breakdown property and the energy storage performance of the dielectric film can be further improved.
  • the present invention provides a method of preparing the above-described barium ferrite-based dielectric film for high-density energy storage, according to an embodiment of the present invention, the method comprising:
  • the barium ferrite-based ceramic target is subjected to pulsed laser deposition treatment and annealing treatment to obtain a barium ferrite-based dielectric film for high-density energy storage.
  • a method for preparing a barium ferrite-based dielectric film for high-density energy storage produces iron by mixing Bi 2 O 3 , Fe 2 O 3 , SrCO 3 , TiO 2 and transition element oxide MeO
  • the acid-based raw material and the doping of the transition element can reduce the leakage of the barium ferrite-based dielectric film; by calcining the barium ferrite-based powder, a series of physical and chemical reactions are generated, which can improve the barium ferrite-based powder.
  • the composition and its structure improve the performance of the barium ferrite-based powder; the barium ferrite-based dielectric film obtained by the method for high-density energy storage is characterized by lead-free environmental protection, high pressure resistance, and excellent energy storage performance.
  • Barium ferrite has a strong ferroelectricity and its spontaneous polarization intensity can reach 100 ⁇ C/cm 2 , which is an excellent substitute for lead-containing ferroelectric materials.
  • Barium titanate is a precursor type ferroelectric, which is a paraelectric phase at normal temperature and has the characteristics of low dielectric loss and small leakage current.
  • the two are formed into a solid solution (1-x)BiFeO 3 -xSrTiO 3 (x is a mole fraction, 0 ⁇ x ⁇ 1), and the breakdown of the prepared dielectric film is achieved by adjusting the value of x and adopting appropriate preparation methods and parameters.
  • the field strength can reach 3 ⁇ 4.5MV/cm
  • the energy storage density can reach up to 70.3J/cm 3
  • it has 70% high energy storage efficiency.
  • this barium ferrite-based dielectric film has a large dielectric constant, small dielectric loss, high breakdown field strength and excellent energy storage performance, and is a promising application for embedded capacitors. Materials in the fields of electrostatic energy storage components, pulse power technology, etc.
  • the method of preparing a barium ferrite-based dielectric film for high-density energy storage may further have the following additional features:
  • Me in the transition element oxide is at least one selected from the group consisting of Mn, Sc, Cr, Ni, and Nb.
  • the composition of the barium ferrite-based raw material is (1-x)Bi 1.1 Fe (1-y) Me y O 3 xSrTiO 3 , wherein 0 ⁇ x ⁇ 1, 0.001 ⁇ y ⁇ 0.02.
  • the organic solvent is at least one selected from the group consisting of anhydrous ethanol, propanol, isopropanol, and ethylene glycol.
  • the time of the ball milling process is 11-13 hours. Thereby, it is advantageous to obtain a barium ferrite-based powder.
  • the barium ferrite-based powder in step (2), has a particle size of from 100 to 500 nm. Thereby, it is advantageous to obtain a barium ferrite-based powder.
  • the pre-firing treatment has a temperature of 750-800 degrees Celsius and a time of 3.5-4.5 hours. Thereby, it is advantageous to obtain a barium ferrite-based ceramic powder.
  • the binder is selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol, polyethylene glycol, tetraethyl orthosilicate, and hydroxypropyl methylcellulose. At least one of them. Thereby, it is advantageous to obtain a barium ferrite-based ceramic wafer.
  • step (4) the pressure of the tableting process is 10-14 MPa. Thereby, it is advantageous to obtain a barium ferrite-based ceramic wafer.
  • the barium ferrite-based ceramic disc in step (4), has a diameter of 0.8-1.2 inches and a thickness of 3-6 mm. Thereby, it is advantageous to obtain a barium ferrite-based ceramic wafer.
  • the temperature of the burying treatment is 1050-1150 degrees Celsius and the time is 35-45 minutes.
  • the parameters of the pulsed laser deposition process are: the reaction chamber has a background vacuum of not more than 5 ⁇ 10 -6 mbar, and the deposition substrate temperature is 700- At 800 degrees Celsius, the partial pressure of oxygen in the chamber is 1-5 Pa, the flow rate of oxygen is 1-10 sccm, and the laser energy is 1-2.5 J/cm 2 .
  • the energy storage performance of the barium ferrite-based dielectric film can be further improved.
  • the annealing treatment in step (6), has a temperature of 450-550 degrees Celsius, an oxygen partial pressure of 200-800 mbar, and an annealing treatment time of 25-35 minutes.
  • the energy storage performance of the barium ferrite-based dielectric film can be further improved.
  • the present invention provides an energy storage device comprising the above-described barium ferrite-based dielectric film for high-density energy storage or iron prepared for high-density energy storage as described above.
  • a barium ferrite-based dielectric film for high-density energy storage obtained by a method of acid-based dielectric thin film.
  • FIG. 1 is a schematic flow chart of a method for preparing a barium ferrite-based dielectric film for high-density energy storage according to an embodiment of the present invention
  • Example 2 is a schematic view showing the structure and test of a ruthenium ferrite-based dielectric film of Example 1-6;
  • Example 3 is a cross-sectional scanning electron micrograph of the barium ferrite-based dielectric film obtained in Example 1;
  • Example 4 is a graph showing dielectric constant and dielectric loss spectrum of a barium ferrite-based dielectric film prepared in Example 1-3;
  • Example 5 is a breakdown field intensity distribution spectrum of a barium ferrite-based dielectric film prepared in Example 1-3;
  • Example 6 is a storage density spectrum of a barium ferrite-based dielectric film prepared in Example 1-3;
  • FIG. 7 is a hysteresis loop spectrum of a barium ferrite-based dielectric film prepared in Example 3.
  • FIG. 7 is a hysteresis loop spectrum of a barium ferrite-based dielectric film prepared in Example 3.
  • the present invention provides a barium ferrite-based dielectric film for high density energy storage.
  • the chemical composition of the dielectric film is of the formula (1-x)BiFeO 3 - xSrTiO 3 , wherein x is a mole fraction and 0 ⁇ x ⁇ 1.
  • bismuth ferrite (BiFeO 3 ) is a kind of multi-iron material, which has ferroelectricity and antiferromagneticity, accompanied by weak ferromagnetism, and its ferroelectricity is caused by the fact that Bi ions have lone pair electrons.
  • its iron electrodeposition is higher than 100uC/cm 2 , but it is difficult to prepare pure barium ferrite, in which there are secondary phases and various defects, which makes it difficult to measure its true iron polarization, usually in iron.
  • the iron polarization measured in the strontium ceramic is only a few uC/cm 2 .
  • Barium titanate (SrTiO 3 ) has a typical perovskite structure and is a widely used electronic functional ceramic material. It has the advantages of high dielectric constant, low dielectric loss and good thermal stability. It is widely used in electronics. Machinery and ceramic industry. Thus, the two forms a solid solution (1-x)BiFeO 3 -xSrTiO 3 (x is a mole fraction, 0 ⁇ x ⁇ 1), and by controlling the value of x, the breakdown field strength of the obtained dielectric film can reach 3 ⁇ 4.5MV/cm, the storage density is up to 70.3J/cm 3 and has a high energy storage efficiency of 70%.
  • this barium ferrite-based dielectric film has a large dielectric constant, small dielectric loss, high breakdown field strength and excellent energy storage performance, and is a promising application for embedded capacitors. Materials in the fields of electrostatic energy storage components, pulse power technology, etc.
  • the thickness of the barium ferrite-based dielectric film for high-density energy storage is not particularly limited, and those skilled in the art can select according to actual needs, according to a specific embodiment of the present invention,
  • the barium ferrite-based dielectric film for high-density energy storage may have a thickness of 150 nm to 2 ⁇ m.
  • the inventors have found that if the thickness of the barium ferrite-based dielectric film is too low, the insulation of the barium ferrite-based dielectric film is deteriorated, which is disadvantageous for the improvement of breakdown and energy storage performance, and the thickness of the barium ferrite-based dielectric film. Too high is not conducive to the miniaturization of energy storage devices. Therefore, the thickness of the barium ferrite-based dielectric film proposed by the present application can significantly improve the insulation of the barium ferrite-based dielectric film, and is advantageous for miniaturization of the energy storage device.
  • the barium ferrite-based dielectric film for high-density energy storage is subjected to transition element doping at the Fe site.
  • the Fe element is susceptible to the conversion of Fe 3+ ⁇ Fe 2+ and generates a large amount of oxygen vacancies, resulting in an increase in leakage current of the material.
  • the transition element at the Fe site the conversion of Fe element can be suppressed, and the insulating property of the barium ferrite-based dielectric film can be improved, thereby further improving the energy storage performance.
  • the doping amount of the transition element is not particularly limited, and those skilled in the art may select according to actual needs.
  • the doping amount of the transition element may be 0.1. Wt% - 2.0 wt%. The inventors have found that if the doping amount of the transition element is too low, the effect of suppressing the transformation of Fe element is not obvious, which is disadvantageous for improving the insulating property of the barium ferrite-based dielectric film. If the doping amount of the transition element is too high, it will lead to the appearance of the transition element impurity phase, and is not conducive to the improvement of the insulation properties and energy storage properties of the barium ferrite-based dielectric film. Thus, the doping amount of the transition element proposed by the present application can significantly improve the insulating properties and energy storage properties of the barium ferrite-based dielectric film.
  • the type of the doping element is not particularly limited, and those skilled in the art may select according to actual needs.
  • the doping element may be selected from Mn. At least one of Sc, Cr, Ni, Nb. The inventors have found that the doping of such transition elements can enhance the insulating properties of the barium ferrite-based dielectric film, thereby significantly improving the energy storage performance of the dielectric film.
  • the present invention provides a method of preparing the above-described barium ferrite-based dielectric film for high-density energy storage. According to an embodiment of the present invention, referring to FIG. 1, the method includes:
  • Bi 2 O 3 , Fe 2 O 3 , SrCO 3 , TiO 2 and a transition element oxide MeO are mixed to obtain a barium ferrite-based raw material.
  • Bi 2 O 3 , Fe 2 O 3 , SrCO 3 , TiO 2 and the transition element oxide MeO can be sufficiently mixed to obtain a solid solution (1-x)BiFeO 3 -xSrTiO 3 (x is a mole fraction, 0 ⁇ x ⁇ 1).
  • x is a mole fraction, 0 ⁇ x ⁇ 1).
  • the inventors have found that barium ferrite has a strong ferroelectricity and its spontaneous polarization intensity can reach 100 ⁇ C/cm 2 , which is an excellent substitute for lead-containing ferroelectric materials.
  • Barium titanate is a precursor type ferroelectric, which is a paraelectric phase at normal temperature and has the characteristics of low dielectric loss and small leakage current.
  • the formed solid solution (1-x)BiFeO 3 -xSrTiO 3 (x is a mole fraction, 0 ⁇ x ⁇ 1) can be prepared by adjusting the value of x and adopting appropriate preparation methods and parameters to prepare a barium ferrite-based dielectric film.
  • the prepared dielectric film has a breakdown field strength of 3 to 4.5 MV/cm, a storage density of up to 70.3 J/cm 3 , and a high energy storage efficiency of 70%, and the doping of the transition element Me reduces iron.
  • the acid-based dielectric film is leak-guided to further improve its energy storage performance.
  • Me in the transition element oxide is not particularly limited, and those skilled in the art may select according to actual needs.
  • Me in the transition element oxide may be It is at least one selected from the group consisting of Mn, Sc, Cr, Ni, and Nb. The inventors have found that the doping of this type of transition element Me can significantly reduce the leakage conductance of the barium ferrite-based dielectric film, thereby further improving the energy storage performance of the resulting dielectric film.
  • the composition of the barium ferrite-based raw material is not particularly limited, and those skilled in the art may select according to actual needs.
  • the composition of the barium ferrite-based raw material may be (1-x)Bi 1.1 Fe (1-y) Me y O 3 xSrTiO 3 , wherein 0 ⁇ x ⁇ 1, 0.001 ⁇ y ⁇ 0.02.
  • the inventors have found that as the proportion of SrTiO 3 increases, the ferroelectric properties of the barium ferrite-based dielectric film are weakened and the polarization ability is lowered, but the insulation and the breakdown field strength are improved.
  • the proportion of SrTiO 3 is 60%, the total performance of the barium ferrite-based dielectric film is the best, the breakdown field strength can reach 3.85MV/cm, the storage density can reach 70.3J/cm 3 , and it has 70% high. Energy storage efficiency. Among them, an excess of 10% of Bi can make up for volatilization.
  • the barium ferrite-based raw material and the organic solvent are sequentially subjected to ball milling, drying, and sieving treatment to obtain a barium ferrite-based powder.
  • the contact area of each component in the barium ferrite-based raw material can be further increased.
  • the type of the organic solvent is not particularly limited, and those skilled in the art may select according to actual needs.
  • the organic solvent may be selected from anhydrous ethanol, and At least one of water ethanol, propanol, isopropanol, and ethylene glycol.
  • the time of the ball milling process is not particularly limited, and those skilled in the art may select according to actual needs.
  • the ball milling process may take 11-13 hours. .
  • the inventors have found that if the ball milling time is too short, the barium ferrite-based raw material particles are too large in size to be sufficiently mixed; and if the ball milling time is too long, the processing cost is increased, and the particle size of the barium ferrite-based raw material does not continue. Reduced. Therefore, the ball milling treatment time proposed by the present application is advantageous for the mixing of the barium ferrite-based raw materials and the processing cost.
  • the particle size of the barium ferrite-based powder is not particularly limited, and those skilled in the art can select according to actual needs.
  • the barium ferrite-based powder The particle size can be from 100 to 500 nm. The inventors have found that if the particle size of the barium ferrite-based powder is too small, the surface adsorption force is too large, molding is difficult, and the processing cost is high; and if the particle size of the barium ferrite-based powder is too large, the components are insufficient. Mixed and insufficient sintering activity. Thus, the particle size proposed in the present application ensures that the barium ferrite-based powder has suitable adsorption and sintering activity.
  • the barium ferrite-based powder is subjected to a calcination treatment to obtain a barium ferrite-based ceramic powder.
  • the inventors have found that by calcining the barium ferrite-based powder, a series of physical and chemical reactions are generated to eliminate volatile organic compounds, crystal water, decomposition products, etc., and the raw material particles are densified, thereby improving the barium ferrite base.
  • the composition of the powder and its structure reduce the volume shrinkage of the subsequent sintering process and improve the performance of the product.
  • the conditions of the calcination treatment are not particularly limited, and those skilled in the art may select according to actual needs.
  • the temperature of the calcination treatment may be 750-780. Celsius, the time can be 3.5-4.5 hours.
  • the inventors have found that if the calcination time is too short and the temperature is too low, volatile organic compounds, crystal water, decomposition products, and the like cannot be sufficiently excluded; and if the calcination time is too long and the temperature is too high, the processing cost is high and may occur. side effects.
  • the use of the calcination treatment conditions proposed in the present application is advantageous in sufficiently eliminating volatile substances in the barium ferrite-based powder and reducing the processing cost.
  • the barium ferrite-based ceramic powder and the binder are subjected to granulation and tableting treatment to obtain a barium ferrite-based ceramic wafer.
  • a barium ferrite-based ceramic wafer satisfying the pulsed laser deposition method can be obtained.
  • the type of the adhesive is not particularly limited, and those skilled in the art can select according to actual needs.
  • the adhesive may be selected from polyvinyl alcohol. At least one of polyethylene glycol, ethyl orthosilicate, and hydroxypropyl methylcellulose.
  • the pressure of the tableting treatment is not particularly limited, and those skilled in the art can select according to actual needs.
  • the pressure of the tableting treatment may be 10- 14MPa. The inventors have found that if the pressure of the tableting treatment is too low, the density of the pressed barium ferrite-based ceramic disc is not ideal; and if the pressure of the tableting treatment is too high, the risk is likely to occur, and after the pressure is relieved, The elastic rebound of the barium ferrite-based ceramic disc is excessively large to cause spallation.
  • the pressure of the tableting treatment proposed by the present application is advantageous for obtaining a high quality barium ferrite-based ceramic wafer.
  • the barium ferrite-based ceramic disc may have a diameter of 0.8 to 1.2 inches and a thickness of 4 to 6 mm.
  • the barium ferrite-based ceramic wafer is subjected to burying treatment to obtain a barium ferrite-based ceramic target.
  • the inventors have found that burying the barium ferrite-based ceramic wafer can reduce the volatilization of Bi in the sintering process, and is beneficial to improve the growth quality and energy storage performance of the barium ferrite-based dielectric film.
  • the conditions of the immersion treatment are not particularly limited, and those skilled in the art may select according to actual needs.
  • the temperature of the burying treatment may be 1050-1150. Celsius, the time can be 35-45 minutes. The inventors have found that if the buried temperature is too low and the time is too short, the sintering of the barium ferrite-based ceramic target will be insufficient, the reaction will be incomplete, and the target performance will be poor. If the buried temperature is too high and the time is too long, The preparation cost is increased, and the excessive growth of the crystal grains and the secondary recrystallization are liable to occur, resulting in deterioration of the target performance. Therefore, the burying treatment conditions proposed by the present application can significantly improve the performance of the strontium ferrite-based ceramic target while reducing the preparation cost.
  • the barium ferrite-based ceramic target is subjected to pulsed laser deposition treatment and annealing treatment to obtain a barium ferrite-based dielectric film for high-density energy storage.
  • the barium ferrite-based ceramic target bombarded by laser is used to diffuse the composition to the conductive single crystal substrate at a stoichiometric ratio, and an epitaxial dielectric film is prepared under suitable substrate temperature, oxygen partial pressure and annealing conditions.
  • the conductive single crystal substrate is an epitaxial perovskite ABO 3 selected from a single crystal selected from the group consisting of pure barium titanate (SrTiO 3 ), lanthanum aluminate (LaAlO 3 ), magnesium aluminate (MgAl 2 O 4 ), and magnesium oxide.
  • a structural conductive film such as lanthanum nickel hydride (LaNiO 3 ), lanthanum manganate, lanthanum cobaltite, or yttrium-doped barium titanate single crystal.
  • the parameters of the pulsed laser deposition process are not particularly limited, and those skilled in the art can select according to actual needs.
  • the parameters of the pulsed laser deposition process may be:
  • the background vacuum of the reaction chamber is not higher than 5 ⁇ 10 -6 mbar
  • the substrate temperature during deposition is 700-800 ° C
  • the partial pressure of oxygen in the chamber is 1-5 Pa
  • the flow rate of oxygen is 1-10 sccm
  • the laser energy is 1- 2.5J/cm 2 .
  • the barium ferrite-based dielectric film is epitaxially grown at a suitable speed, and the obtained barium ferrite-based dielectric film has high quality, which is advantageous for improving the dielectric and energy storage properties of the film.
  • the conditions of the annealing treatment are not particularly limited, and those skilled in the art may select according to actual needs.
  • the annealing temperature may be 450-550 degrees Celsius.
  • the oxygen partial pressure may be 200-800 mbar, and the annealing treatment time may be 25-35 min. The inventors have found that under the above parameters, the oxygen vacancies in the barium ferrite-based dielectric film are fully compensated, which is beneficial to improve the insulating ability and energy storage performance of the film.
  • a method for preparing a barium ferrite-based dielectric film for high-density energy storage produces a barium ferrite-based material by mixing BiFeO 3 with SrTiO 3 and a transition element Me, and the doping of the transition element can be reduced.
  • the barium ferrite-based dielectric film is leak-guided; by calcining the barium ferrite-based powder, a series of physical and chemical reactions are generated, which can improve the composition and structure of the barium ferrite-based powder and improve the barium ferrite-based powder.
  • the performance of the method is characterized by high-density energy storage of barium ferrite-based dielectric film characterized by lead-free environmental protection, high pressure resistance and excellent energy storage performance.
  • Barium ferrite has a strong ferroelectricity and its spontaneous polarization intensity can reach 100 ⁇ C/cm 2 , which is an excellent substitute for lead-containing ferroelectric materials.
  • Barium titanate is a precursor type ferroelectric, which is a paraelectric phase at normal temperature and has the characteristics of low dielectric loss and small leakage current.
  • the two are formed into a solid solution (1-x)BiFeO 3 -xSrTiO 3 (x is a mole fraction, 0 ⁇ x ⁇ 1), and the breakdown of the prepared dielectric film is achieved by adjusting the value of x and adopting appropriate preparation methods and parameters.
  • the field strength can reach 3 ⁇ 4.5MV/cm
  • the energy storage density can reach up to 70.3J/cm 3
  • it has 70% high energy storage efficiency.
  • this barium ferrite-based dielectric film has a large dielectric constant, small dielectric loss, high breakdown field strength and excellent energy storage performance, and is a promising application for embedded capacitors. Materials in the fields of electrostatic energy storage components, pulse power technology, etc.
  • the present invention provides an energy storage device comprising the above-described barium ferrite-based dielectric film for high-density energy storage or according to the above preparation, in accordance with an embodiment of the present invention.
  • a barium ferrite-based dielectric film for high-density energy storage obtained by a high-density energy storage method of barium ferrite-based dielectric film.
  • the energy storage performance of the energy storage device can be significantly improved.
  • the features and advantages described above for the barium ferrite-based dielectric film for high-density energy storage and the method for preparing a barium ferrite-based dielectric film for high-density energy storage are equally applicable to the energy storage.
  • the energy storage device may be a dielectric capacitor, an embedded capacitor, an electrostatic energy storage component, a pulse power component, or a device further developed and assembled based on the above device.
  • a metal round electrode (having a diameter of 100 to 400 ⁇ m and a thickness of about 100 nm) was prepared by a direct current ion sputtering method on a film sample.
  • the dielectric performance test was performed using the E4990A impedance analyzer manufactured by Agilent, USA.
  • the breakdown field strength and ferroelectric hysteresis loop were tested using the Precision Premier II ferroelectric tester from Radiant Tech., USA.
  • the energy density and efficiency were determined by the hysteresis.
  • the loop calculation is obtained.
  • the structure and test schematic of the barium ferrite-based dielectric film of the present invention are shown in FIG.
  • a 5% (mass%) concentration PVA solution was added to the barium ferrite-based ceramic powder to be granulated, and pressed into a barium ferrite-based ceramic disc having a diameter of about 1 inch and a thickness of about 5 mm under a 12 MPa tablet press. After the PVA was removed by heat preservation, the barium ferrite-based ceramic wafer was sealed and buried at 1100 ° C for 40 min to obtain a barium ferrite-based ceramic target.
  • Pulsed laser deposition technique was used to bombard the barium ferrite-based ceramic target by laser, and the composition was diffused to the ytterbium-doped barium titanate conductive single crystal substrate at a stoichiometric ratio to prepare an epitaxial dielectric film.
  • the parameters of the pulsed laser deposition technique include: the vacuum of the reaction chamber is not higher than 5 ⁇ 10 -6 mbar; the substrate temperature at deposition is 700 ° C, the partial pressure of oxygen in the chamber is 1.3 Pa, and the flow rate of oxygen is 1.5 sccm. The energy is 1.7 J/cm 2 . After the deposition, the film was annealed at 500 ° C, 500 mbar oxygen partial pressure for 30 min, and then cooled to room temperature at a rate of 10 ° C / min.
  • the obtained barium ferrite-based dielectric film has a thickness of about 450 nm.
  • Figure 3 shows a scanning electron micrograph of the barium ferrite-based dielectric film. It can be found that the film has good epitaxial quality, small surface roughness, and the film is dense, uniform, and free. Defects are beneficial to the improvement of insulation capacity and energy storage performance.
  • the properties of the barium ferrite-based dielectric film reached the following indexes: the dielectric constant and loss of the barium ferrite-based dielectric film at 1 kHz were 255 and 0.028, the breakdown field strength was 2.77 MV/cm, and the storage density reached 21.8 J. /cm 3 .
  • a 5% (mass%) concentration PVA solution was added to the barium ferrite-based ceramic powder to be granulated, and pressed into a barium ferrite-based ceramic disc having a diameter of about 1 inch and a thickness of about 5 mm under a 12 MPa tablet press. After the PVA was removed by heat preservation, the barium ferrite-based ceramic wafer was sealed and buried at 1100 ° C for 40 min to obtain a barium ferrite-based ceramic target.
  • Pulsed laser deposition technique was used to bombard the barium ferrite-based ceramic target by laser, and the composition was diffused to the ytterbium-doped barium titanate conductive single crystal substrate at a stoichiometric ratio to prepare an epitaxial dielectric film.
  • the parameters of the pulsed laser deposition technique include: the vacuum of the reaction chamber is not higher than 5 ⁇ 10 -6 mbar; the substrate temperature at deposition is 700 ° C, the partial pressure of oxygen in the chamber is 1.3 Pa, and the flow rate of oxygen is 1.5 sccm. The energy is 1.7 J/cm 2 . After the deposition, the film was annealed at 500 ° C, 500 mbar oxygen partial pressure for 30 min, and then cooled to room temperature at a rate of 10 ° C / min.
  • the obtained barium ferrite-based dielectric film has a thickness of about 550 nm.
  • the properties of the barium ferrite-based dielectric film reached the following indexes: the dielectric constant and loss of the barium ferrite-based dielectric film at 300 kHz were 300 and 0.029, the breakdown field strength was 3.38 MV/cm, and the storage density reached 35.6 J. /cm 3 .
  • a 5% (mass%) concentration PVA solution was added to the barium ferrite-based ceramic powder to be granulated, and pressed into a barium ferrite-based ceramic disc having a diameter of about 1 inch and a thickness of about 5 mm under a 12 MPa tablet press. After the PVA was removed by heat preservation, the barium ferrite-based ceramic wafer was sealed and buried at 1100 ° C for 40 min to obtain a barium ferrite-based ceramic target.
  • Pulsed laser deposition technique was used to bombard the barium ferrite-based ceramic target by laser, and the composition was diffused to the ytterbium-doped barium titanate conductive single crystal substrate at a stoichiometric ratio to prepare an epitaxial dielectric film.
  • the parameters of the pulsed laser deposition technique include: the vacuum of the reaction chamber is not higher than 5 ⁇ 10 -6 mbar; the substrate temperature at deposition is 700 ° C, the partial pressure of oxygen in the chamber is 1.3 Pa, and the flow rate of oxygen is 1.5 sccm. The energy is 1.7 J/cm 2 . After the deposition, the film was annealed at 500 ° C, 500 mbar oxygen partial pressure for 30 min, and then cooled to room temperature at a rate of 10 ° C / min.
  • the prepared barium ferrite-based dielectric film has a thickness of about 600 nm.
  • Figure 7 shows the hysteresis loop of the barium ferrite based dielectric film at different electric field strengths.
  • the properties of the barium ferrite-based dielectric film reached the following indexes: the dielectric constant and loss of the barium ferrite-based dielectric film at 1 kHz were 256 and 0.022, the breakdown field strength was 3.85 MV/cm, and the storage density reached 70.3 J. /cm 3 , energy storage efficiency is as high as 70%.
  • a 5% (mass%) concentration PVA solution was added to the barium ferrite-based ceramic powder to be granulated, and pressed into a barium ferrite-based ceramic disc having a diameter of about 1 inch and a thickness of about 5 mm under a 12 MPa tablet press. After the PVA was removed by heat preservation, the barium ferrite-based ceramic wafer was sealed and buried at 1100 ° C for 40 min to obtain a barium ferrite-based ceramic target.
  • Pulsed laser deposition technique was used to bombard the barium ferrite-based ceramic target by laser, and the composition was diffused to the ytterbium-doped barium titanate conductive single crystal substrate at a stoichiometric ratio to prepare an epitaxial dielectric film.
  • the parameters of the pulsed laser deposition technique include: the background vacuum of the reaction chamber is not higher than 5 ⁇ 10 -6 mbar; the substrate temperature is 700 degrees Celsius during deposition, the oxygen partial pressure of the chamber is 2.6 Pa, the oxygen flow rate is 2 sccm, and the laser energy It is 1.4J/cm 2 .
  • the film was annealed at 500 ° C, 800 mbar oxygen partial pressure for 30 min, and then cooled to room temperature at a rate of 10 ° C / min.
  • the prepared barium ferrite-based dielectric film has a thickness of about 500 nm, and the performance of the barium ferrite-based dielectric film reaches the following index: at a test field strength of 2 MV/cm, the storage density reaches 20.9 J/cm 3 , and the energy storage efficiency It is 52%.
  • a 5% (mass%) concentration PVA solution was added to the barium ferrite-based ceramic powder to be granulated, and pressed into a barium ferrite-based ceramic disc having a diameter of about 1 inch and a thickness of about 5 mm under a 12 MPa tablet press. After the PVA was removed by heat preservation, the barium ferrite-based ceramic wafer was sealed and buried at 1100 ° C for 40 min to obtain a barium ferrite-based ceramic target.
  • Pulsed laser deposition technique was used to bombard the barium ferrite-based ceramic target by laser, and the composition was diffused to the ytterbium-doped barium titanate conductive single crystal substrate at a stoichiometric ratio to prepare an epitaxial dielectric film.
  • the parameters of the pulsed laser deposition technique include: the vacuum of the reaction chamber is not higher than 5 ⁇ 10 -6 mbar; the substrate temperature during deposition is 700 ° C, the partial pressure of oxygen in the chamber is 1.3 Pa, and the flow rate of oxygen is 1 sccm. It is 1.7 J/cm 2 . After the deposition, the film was annealed at 500 ° C, 500 mbar oxygen partial pressure for 30 min, and then cooled to room temperature at a rate of 10 ° C / min.
  • the obtained barium ferrite-based dielectric film has a thickness of about 500 nm, and the performance of the barium ferrite-based dielectric film reaches the following indexes: the dielectric constant and loss of the barium ferrite-based dielectric film at 1 kHz are 187 and 0.020, respectively, and the breakdown field The intensity is 4.46 MV/cm, the storage density reaches 70.0 J/cm 3 , and the energy storage efficiency is as high as 68%.
  • a 5% (mass%) concentration PVA solution was added to the barium ferrite-based ceramic powder to be granulated, and pressed into a barium ferrite-based ceramic disc having a diameter of about 1 inch and a thickness of about 5 mm under a 12 MPa tablet press. After the PVA was removed by heat preservation, the barium ferrite-based ceramic wafer was sealed and buried at 1100 ° C for 40 min to obtain a barium ferrite-based ceramic target.
  • Pulsed laser deposition technique was used to bombard the barium ferrite-based ceramic target by laser, and the composition was diffused to the ytterbium-doped barium titanate conductive single crystal substrate at a stoichiometric ratio to prepare an epitaxial dielectric film.
  • the parameters of the pulsed laser deposition technique include: the vacuum of the reaction chamber is not higher than 5 ⁇ 10 -6 mbar; the substrate temperature during deposition is 800 degrees Celsius, the partial pressure of oxygen in the chamber is 2.6 Pa, and the flow rate of oxygen is 2 sccm, laser energy It is 1.6J/cm 2 .
  • the film was annealed at 500 ° C, 800 mbar oxygen partial pressure for 30 min, and then cooled to room temperature at a rate of 10 ° C / min.
  • the obtained barium ferrite-based dielectric film has a thickness of about 540 nm, and the performance of the barium ferrite-based dielectric film reaches the following indexes: the dielectric constant and loss of the barium ferrite-based dielectric film at 1 kHz are 275 and 0.020, respectively, and the breakdown field Under the condition of 3.6 MV/cm, the energy storage density reached 51 J/cm 3 and the energy storage efficiency reached 64%.

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Abstract

一种用于高密度储能的铁酸铋基电介质薄膜及其制备方法和应用，该电介质薄膜化学成分通式为（1-x）BiFeO 3-xSrTiO 3，其中，x为摩尔分数，且0<x<1。

Description

用于高密度储能的铁酸铋基电介质薄膜及其制备方法和应用 技术领域
本发明属于电介质材料领域，具体而言，本发明涉及用于高密度储能的铁酸铋基电介质薄膜及其制备方法和应用。
背景技术
电介质电容器作为主要的无源储能器件，以其快速的充放电速度和超高的功率密度，广泛应用于电子电路中，可以实现隔直通交、耦合、旁路、滤波、调谐回路、能量转换等功能。然而其较低的储能密度成为其进一步发展和应用的瓶颈。目前商业化的电介质材料储能密度仅约2J/cm 3，与电化学电容器或电池相比低了一至两个数量级。因此，探索具有高储能密度的电介质材料一直是该领域研究热点。
陶瓷薄膜电介质具有大的介电常数和高的击穿场强，成为最有希望获得高储能密度的电介质材料体系，同时由于其体积小、机械性能好、耐高温性能优异，有望在器件小型化、集成化和极端条件下获得应用。目前在一大类锆钛酸铅(PZT)基薄膜电介质中已经实现了30～60J/cm 3的高储能密度。其中具有代表性的如：Zhongqiang Hu等利用化学沉积法制备的Pb 0.96La 0.04Zr 0.98Ti 0.02O 3反铁电薄膜具有61J/cm 3的储能密度，并在室温到225摄氏度范围内保持性能稳定；Guangliang Hu等利用脉冲激光沉积方法制备的Pb 0.92La 0.08Zr 0.52Ti 0.48O 3弛豫铁电薄膜则可以实现31J/cm 3的储能密度，并在室温到180摄氏度范围内保持性能稳定。但是这些材料中含有的铅对人体健康和环境有较大危害，废弃后不易处理。因此，开发具有大介电常数、高击穿场强、高储能密度和良好温度稳定性的无铅薄膜电介质材料成为该领域当前的急迫任务。
发明内容
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本发明的一个目的在于提出一种用于高密度储能的铁酸铋基电介质薄膜及其制备方法和应用。该电介质薄膜具有优异的储能性能，储能密度可达70.3J/cm 3，并具有70％的高储能效率。
在本发明的一个方面，本发明提出了一种用于高密度储能的铁酸铋基电介质薄膜，根据本发明的实施例，所述电介质薄膜化学成分通式为(1-x)BiFeO 3-xSrTiO 3，其中，x为摩尔分数，且0<x<1。
发明人发现，铁酸铋(BiFeO 3)属于多铁材料的一种，具有铁电性和反铁磁性，并伴随弱的铁磁性，其铁电性是由于Bi离子具有孤对电子引起的，理论上其铁电极化高于 100uC/cm 2，但是由于很难制备出纯的铁酸铋，其中存在二次相和各种缺陷，导致很难测出其真实的铁电极化，通常在铁酸铋陶瓷中测得的铁电极化只有几个uC/cm 2；钛酸锶(SrTiO 3)具有典型的钙钛矿型结构，是一种用途广泛的电子功能陶瓷材料，具有介电常数高、介电损耗低、热稳定性好等优点，广泛应用于电子、机械和陶瓷工业。由此，将两者形成固溶体(1-x)BiFeO 3-xSrTiO 3(x为摩尔分数，0<x<1)，通过调控x的值，所得到的电介质薄膜具有优异的铁电性能和绝缘性质，其击穿场强可达3～4.5MV/cm，储能密度最高可达70.3J/cm 3，并具有70％的高储能效率。实验证明这种铁酸铋基电介质薄膜兼具较大的介电常数、较小的介电损耗、较高的击穿场强和优异的储能性能，是一种有希望应用于嵌入式电容器、静电储能元器件、脉冲功率技术等领域的材料。
另外，根据本发明上述实施例的用于高密度储能的铁酸铋基电介质薄膜还可以具有如下附加特征：
在本发明的一些实施例中，所述用于高密度储能的铁酸铋基电介质薄膜的厚度为150nm-2μm。由此，有利于改善电介质薄膜的生长质量、提高电介质薄膜的储能性能。
在本发明的一些实施例中，所述用于高密度储能的铁酸铋基电介质薄膜在Fe位进行过渡元素掺杂。由此，可改善薄膜的绝缘性质，进一步提高电介质薄膜的储能性能。
在本发明的一些实施例中，所述过渡元素的掺杂量为0.1wt％-2.0wt％。由此，可进一步提高电介质薄膜的击穿性质和储能性能。
在本发明的再一个发明，本发明提出了一种制备上述用于高密度储能的铁酸铋基电介质薄膜的方法，根据本发明的实施例，所述方法包括：
(1)将Bi 2O 3、Fe 2O 3、SrCO 3、TiO 2和过渡元素氧化物MeO进行混合配料，以便得到铁酸铋基原料；
(2)将所述铁酸铋基原料和有机溶剂依次进行球磨、干燥和筛分处理，以便得到铁酸铋基粉末；
(3)将所述铁酸铋基粉末进行预烧处理，以便得到铁酸铋基陶瓷粉体；
(4)将所述铁酸铋基陶瓷粉体和粘合剂进行造粒和压片处理，以便得到铁酸铋基陶瓷圆片；
(5)将所述铁酸铋基陶瓷圆片进行埋烧处理，以便得到铁酸铋基陶瓷靶材；
(6)将所述铁酸铋基陶瓷靶材进行脉冲激光沉积处理和退火处理，以便得到用于高密度储能的铁酸铋基电介质薄膜。
根据本发明实施例的制备用于高密度储能的铁酸铋基电介质薄膜的方法通过将Bi 2O 3、Fe 2O 3、SrCO 3、TiO 2和过渡元素氧化物MeO进行混合制备得到铁酸铋基原料，过渡元素的掺杂可降低铁酸铋基电介质薄膜漏导；通过将铁酸铋基粉末进行预烧处理，会产生一系列 的物理化学反应，能改善铁酸铋基粉末的成分及其组织结构，提高铁酸铋基粉末的性能；该方法所得的用于高密度储能的铁酸铋基电介质薄膜的特点是无铅环保、耐高压能力强、具有优异的储能性能。铁酸铋具有很强的铁电性，其自发极化强度可达100μC/cm 2，是含铅铁电材料的优秀替代品。钛酸锶为先兆型铁电体，常温下为顺电相，具有介电损耗低、漏电流小的特点。将两者形成固溶体(1-x)BiFeO 3-xSrTiO 3(x为摩尔分数，0<x<1)，通过调控x的值，并采用适当的制备方法和参数，制备的电介质薄膜的击穿场强可达3～4.5MV/cm，储能密度最高可达70.3J/cm 3，并具有70％的高储能效率。实验证明这种铁酸铋基电介质薄膜兼具较大的介电常数、较小的介电损耗、较高的击穿场强和优异的储能性能，是一种有希望应用于嵌入式电容器、静电储能元器件、脉冲功率技术等领域的材料。
另外，根据本发明上述实施例的制备用于高密度储能的铁酸铋基电介质薄膜的方法还可以具有如下附加特征：
在本发明的一些实施例中，在步骤(1)中，所述过渡元素氧化物中的Me为选自Mn，Sc，Cr，Ni，Nb中的至少之一。由此，有利于提高铁酸铋基电介质薄膜的生长质量和绝缘能力，有利于提高储能性能。
在本发明的一些实施例中，在步骤(1)中，所述铁酸铋基原料的组成为(1-x)Bi 1.1Fe (1-y)Me yO 3xSrTiO 3，其中，0<x<1，0.001<y<0.02。由此，可进一步提高铁酸铋基电介质薄膜的储能性能。
在本发明的一些实施例中，在步骤(2)中，所述有机溶剂为选自无水乙醇、丙醇、异丙醇和乙二醇中的至少一种。由此，有利于得到铁酸铋基粉末。在本发明的一些实施例中，在步骤(2)中，所述球磨处理的时间为11-13小时。由此，有利于得到铁酸铋基粉末。
在本发明的一些实施例中，在步骤(2)中，所述铁酸铋基粉末的粒径为100-500nm。由此，有利于得到铁酸铋基粉末。
在本发明的一些实施例中，在步骤(3)中，所述预烧处理的温度为750-800摄氏度，时间为3.5-4.5小时。由此，有利于得到铁酸铋基陶瓷粉体。
在本发明的一些实施例中，在步骤(4)中，所述粘合剂为选自聚乙烯醇、聚乙烯醇、聚乙二醇、正硅酸乙酯和羟丙基甲基纤维素中的至少一种。由此，有利于得到铁酸铋基陶瓷圆片。
在本发明的一些实施例中，在步骤(4)中，所述压片处理的压力为10-14MPa。由此，有利于得到铁酸铋基陶瓷圆片。
在本发明的一些实施例中，在步骤(4)中，所述铁酸铋基陶瓷圆片的直径为0.8-1.2英寸，厚度为3-6mm。由此，有利于得到铁酸铋基陶瓷圆片。
在本发明的一些实施例中，在步骤(5)中，所述埋烧处理的温度为1050-1150摄氏度， 时间为35-45分钟。由此，有利于得到铁酸铋基陶瓷靶材。
在本发明的一些实施例中，在步骤(6)中，所述脉冲激光沉积处理的参数为：反应腔体本底真空度不高于5×10 -6mbar，沉积时基底温度为700-800摄氏度，腔体氧分压为1-5Pa，通氧气流量为1-10sccm，激光能量为1-2.5J/cm 2。由此，可进一步提高铁酸铋基电介质薄膜的储能性能。
在本发明的一些实施例中，在步骤(6)中，所述退火处理的温度为450-550摄氏度，氧分压为200-800mbar，退火处理的时间为25-35min。由此，可进一步提高铁酸铋基电介质薄膜的储能性能。
在本发明的又一个方面，本发明提出了一种储能器件，所述储能器件包括上述用于高密度储能的铁酸铋基电介质薄膜或采用上述制备用于高密度储能的铁酸铋基电介质薄膜的方法得到的用于高密度储能的铁酸铋基电介质薄膜。由此，可显著提高储能器件的储能性能。
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。
附图说明
本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1是根据本发明一个实施例的制备用于高密度储能的铁酸铋基电介质薄膜的方法流程示意图；
图2是实施例1-6铁酸铋基电介质薄膜的结构及测试示意图；
图3是实施例1所得铁酸铋基电介质薄膜的断面扫描电镜图；
图4为实施例1-3中制备的铁酸铋基电介质薄膜的介电常数和介电损耗谱图；
图5为实施例1-3中制备的铁酸铋基电介质薄膜的击穿场强分布谱图；
图6为实施例1-3中制备的铁酸铋基电介质薄膜的储能密度谱图；
图7为实施例3中制备的铁酸铋基电介质薄膜的电滞回线谱图。
发明详细描述
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。
在本发明的一个方面，本发明提出了一种用于高密度储能的铁酸铋基电介质薄膜，根 据本发明的实施例，上述电介质薄膜化学成分通式为(1-x)BiFeO 3-xSrTiO 3，其中，x为摩尔分数，且0<x<1。
发明人发现，铁酸铋(BiFeO 3)属于多铁材料的一种，具有铁电性和反铁磁性，并伴随弱的铁磁性，其铁电性是由于Bi离子具有孤对电子引起的，理论上其铁电极化高于100uC/cm 2，但是由于很难制备出纯的铁酸铋，其中存在二次相和各种缺陷，导致很难测出其真实的铁电极化，通常在铁酸铋陶瓷中测得的铁电极化只有几个uC/cm 2。钛酸锶(SrTiO 3)具有典型的钙钛矿型结构，是一种用途广泛的电子功能陶瓷材料，具有介电常数高、介电损耗低、热稳定性好等优点，广泛应用于电子、机械和陶瓷工业。由此，将两者形成固溶体(1-x)BiFeO 3-xSrTiO 3(x为摩尔分数，0<x<1)，通过调控x的值，所得到的电介质薄膜的击穿场强可达3～4.5MV/cm，储能密度最高可达70.3J/cm 3，并具有70％的高储能效率。实验证明这种铁酸铋基电介质薄膜兼具较大的介电常数、较小的介电损耗、较高的击穿场强和优异的储能性能，是一种有希望应用于嵌入式电容器、静电储能元器件、脉冲功率技术等领域的材料。
根据本发明的一个实施例，用于高密度储能的铁酸铋基电介质薄膜的厚度并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，用于高密度储能的铁酸铋基电介质薄膜的厚度可以为150nm-2μm。发明人发现，若铁酸铋基电介质薄膜的厚度过低，则铁酸铋基电介质薄膜的绝缘性变差，不利于击穿和储能性能的提升；而若铁酸铋基电介质薄膜的厚度过高，则不利于储能器件的微型化应用。由此，采用本申请提出的铁酸铋基电介质薄膜的厚度可显著提高铁酸铋基电介质薄膜的绝缘性，同时有利于储能器件的微型化应用。
根据本发明的再一个实施例，用于高密度储能的铁酸铋基电介质薄膜在Fe位进行过渡元素掺杂。具体的，铁酸铋基材料中，Fe元素易发生Fe 3+→Fe 2+的转变并且产生大量氧空位，导致材料漏电流增大。通过在Fe位进行过渡元素掺杂，可以抑制Fe元素的转变，提升铁酸铋基电介质薄膜的绝缘性质，从而进一步提升储能性能。
根据本发明的又一个实施例，过渡元素的掺杂量并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，过渡元素的掺杂量可以为0.1wt％-2.0wt％。发明人发现，若过渡元素掺杂量过低，对Fe元素转变的抑制效果不明显，不利于提升铁酸铋基电介质薄膜的绝缘性质。而若过渡元素掺杂量过高，则会导致过渡元素杂相的出现，也不利于提升铁酸铋基电介质薄膜的绝缘性质和储能性能。由此，采用本申请提出的过渡元素的掺杂量可显著提升铁酸铋基电介质薄膜的绝缘性质和储能性能。
根据本发明的又一个实施例，掺杂元素的种类并不受特别限制，本领域技术人员被可以根据实际需要进行选择，根据本发明的一个具体实施例，掺杂元素可以为选自Mn，Sc， Cr，Ni，Nb中的至少之一。发明人发现，该类过渡元素的掺杂可提升铁酸铋基电介质薄膜绝缘性质，从而显著提高该电介质薄膜的储能性能。
在本发明的再一个发明，本发明提出了一种制备上述用于高密度储能的铁酸铋基电介质薄膜的方法，根据本发明的实施例，参考图1，该方法包括：
S100：将BiFeO 3与SrTiO 3和过渡元素Me进行混合配料
该步骤中，Bi 2O 3、Fe 2O 3、SrCO 3、TiO 2和过渡元素氧化物MeO进行混合配料，以便得到铁酸铋基原料。由此，可使Bi 2O 3、Fe 2O 3、SrCO 3、TiO 2和过渡元素氧化物MeO充分混合，得到固溶体(1-x)BiFeO 3-xSrTiO 3(x为摩尔分数，0<x<1)。发明人发现，铁酸铋具有很强的铁电性，其自发极化强度可达100μC/cm 2，是含铅铁电材料的优秀替代品。钛酸锶为先兆型铁电体，常温下为顺电相，具有介电损耗低、漏电流小的特点。形成的固溶体(1-x)BiFeO 3-xSrTiO 3(x为摩尔分数，0<x<1)可通过调控x的值，并采用适当的制备方法和参数，制备得到铁酸铋基电介质薄膜，制备的电介质薄膜的击穿场强可达3～4.5MV/cm，储能密度最高可达70.3J/cm 3，并具有70％的高储能效率，并且过渡元素Me的掺杂可降低铁酸铋基电介质薄膜漏导，从而进一步提高其储能性能。
根据本发明的一个实施例，过渡元素氧化物中的Me并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，过渡元素氧化物中的Me可以为选自Mn，Sc，Cr，Ni，Nb中的至少之一。发明人发现，该类过渡元素Me的掺杂可以显著降低铁酸铋基电介质薄膜漏导，从而进一步提高所得电介质薄膜的储能性能。
根据本发明的再一个实施例，铁酸铋基原料的组成并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，铁酸铋基原料的组成可以为(1-x)Bi 1.1Fe (1-y)Me yO 3xSrTiO 3，其中，0<x<1，0.001<y<0.02。发明人发现，随SrTiO 3的比例增加，铁酸铋基电介质薄膜的铁电性质减弱、极化能力降低，但绝缘性和击穿场强提升。在SrTiO 3的比例为60％时，铁酸铋基电介质薄膜的综合性能最为优异，击穿场强可达3.85MV/cm，储能密度可达70.3J/cm 3，并具有70％的高储能效率。其中，Bi元素过量10％可弥补挥发。
S200：将铁酸铋基原料和有机溶剂依次进行球磨、干燥和筛分处理
该步骤中，将铁酸铋基原料和有机溶剂依次进行球磨、干燥和筛分处理，以便得到铁酸铋基粉末。由此，可进一步增加铁酸铋基原料中各成分的接触面积。
根据本发明的一个实施例，有机溶剂的类型并不受特别限制，本领域的技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，有机溶剂可以为选自无水乙醇、无水乙醇、丙醇、异丙醇和乙二醇中的至少一种。
根据本发明的再一个实施例，球磨处理的时间并不受特别限制，本领域的技术人员可 以根据实际需要进行选择，根据本发明的一个具体实施例，球磨处理的时间可以为11-13小时。发明人发现，若球磨时间过短，则铁酸铋基原料颗粒尺寸过大，难以充分混合；而若球磨时间过长，则加工成本升高，且铁酸铋基原料的颗粒尺寸不会继续减小。由此，采用本申请提出的球磨处理时间有利于铁酸铋基原料混合充分，同时降低加工成本。
根据本发明的又一个实施例，铁酸铋基粉末的粒径并不受特别限制，本领域的技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，铁酸铋基粉末的粒径可以为100-500nm。发明人发现，若铁酸铋基粉末的粒径过小，则其表面吸附力过大，成型困难，且加工成本高；而若铁酸铋基粉末的粒径过大，则各成分无法充分混合，且烧结活性不够。由此，采用本申请提出的粒径可保证铁酸铋基粉末有合适的吸附力和烧结活性。
S300：将铁酸铋基粉末进行预烧处理
该步骤中，将铁酸铋基粉末进行预烧处理，以便得到铁酸铋基陶瓷粉体。发明人发现，通过将铁酸铋基粉末进行预烧处理，将产生一系列的物理化学反应，排除挥发性有机物、结晶水、分解物等，并使原料颗粒致密化，可改善铁酸铋基粉末的成分及其组织结构，减少后续烧结过程的体积收缩，提高制品的性能。
根据本发明的一个实施例，预烧处理的条件并不受特别限制，本领域的技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，预烧处理的温度可以为750-780摄氏度，时间可以为3.5-4.5小时。发明人发现，若预烧时间过短、温度过低，则无法充分排除挥发性有机物、结晶水、分解物等；而若预烧时间过长、温度过高，则加工成本高，且可能产生副反应。由此，采用本申请提出的预烧处理条件有利于充分排除铁酸铋基粉末中的挥发性物质且降低加工成本。
S400：将铁酸铋基陶瓷粉体和粘合剂进行造粒和压片处理
该步骤中，将铁酸铋基陶瓷粉体和粘合剂进行造粒和压片处理，以便得到铁酸铋基陶瓷圆片。由此，可制得满足脉冲激光沉积法的铁酸铋基陶瓷圆片。
根据本发明的一个实施例，粘合剂的类型并不受特别限制，本领域的技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，粘合剂可以为选自聚乙烯醇、聚乙二醇、正硅酸乙酯和羟丙基甲基纤维素中的至少一种。
根据本发明的再一个实施例，压片处理的压力并不受特别限制，本领域的技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，压片处理的压力可以为10-14MPa。发明人发现，若压片处理的压力过低，则压制的铁酸铋基陶瓷圆片的致密度不够理想；而若压片处理的压力过高，则易发生危险、且卸压后可能因为铁酸铋基陶瓷圆片弹性回弹过大产生层裂。由此，采用本申请提出的压片处理的压力有利于得到高品质的铁酸铋基陶瓷圆片。
根据本发明的又一个实施例，铁酸铋基陶瓷圆片的直径可以为0.8-1.2英寸，厚度可以为4-6mm。
S500：将铁酸铋基陶瓷圆片进行埋烧处理
该步骤中，将铁酸铋基陶瓷圆片进行埋烧处理，以便得到铁酸铋基陶瓷靶材。发明人发现，将铁酸铋基陶瓷圆片进行埋烧处理，可以降低烧结过程中Bi元素的挥发，有利于提升铁酸铋基电介质薄膜的生长质量和储能性能。
根据本发明的一个实施例，埋烧处理的条件并不受特别限制，本领域的技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，埋烧处理的温度可以为1050-1150摄氏度，时间可以为35-45分钟。发明人发现，若埋烧温度过低、时间过短，将导致铁酸铋基陶瓷靶材烧结致密度不够，反应不完全，靶材性能差；而若埋烧温度过高、时间过长，则制备成本升高，且易产生晶粒过度长大和二次再结晶，导致靶材性能变差。由此，采用本申请提出的埋烧处理条件可显著提高铁酸铋基陶瓷靶材的性能，同时可降低制备成本。
S600：将铁酸铋基陶瓷靶材进行脉冲激光沉积处理和退火处理
该步骤中，将铁酸铋基陶瓷靶材进行脉冲激光沉积处理和退火处理，以便得到用于高密度储能的铁酸铋基电介质薄膜。具体的，利用激光轰击的铁酸铋基陶瓷靶材，使其成分以化学计量比扩散到导电单晶基底，在合适的基底温度、氧分压和退火条件下制得外延电介质薄膜。导电单晶基底为选自纯钛酸锶(SrTiO 3)、铝酸镧(LaAlO 3)、铝酸镁(MgAl 2O 4)和氧化镁中至少之一的单晶上外延钙钛矿ABO 3结构导电薄膜，如镍酸镧(LaNiO 3)、锰酸镧锶、钴酸镧锶，或者是铌掺杂的钛酸锶单晶。
根据本发明的一个实施例，脉冲激光沉积处理的参数并不受特别限制，本领域的技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，脉冲激光沉积处理的参数可以为：反应腔体本底真空度不高于5×10 -6mbar，沉积时基底温度为700-800摄氏度，腔体氧分压为1-5Pa，通氧气流量为1-10sccm，激光能量为1-2.5J/cm 2。发明人发现，在上述参数下，铁酸铋基电介质薄膜以适宜的速度外延生长，所得的铁酸铋基电介质薄膜质量高，有利于提高薄膜的介电和储能性能。
根据本发明的再一个实施例，退火处理的条件并不受特别限制，本领域的技术人员可以根据实际需要进行选择，根据本发明的一个具体实施例，退火处理的温度可以为450-550摄氏度，氧分压可以为200-800mbar，退火处理的时间可以为25-35min。发明人发现，在上述参数下，铁酸铋基电介质薄膜中的氧空位得到充分弥补，有利于提高薄膜的绝缘能力和储能性能。
根据本发明实施例的制备用于高密度储能的铁酸铋基电介质薄膜的方法通过将BiFeO 3与SrTiO 3和过渡元素Me进行混合制备得到铁酸铋基原料，过渡元素的掺杂可降低铁酸铋 基电介质薄膜漏导；通过将铁酸铋基粉末进行预烧处理，会产生一系列的物理化学反应，能改善铁酸铋基粉末的成分及其组织结构，提高铁酸铋基粉末的性能；该方法所得的用于高密度储能的铁酸铋基电介质薄膜的特点是无铅环保、耐高压能力强、具有优异的储能性能。铁酸铋具有很强的铁电性，其自发极化强度可达100μC/cm 2，是含铅铁电材料的优秀替代品。钛酸锶为先兆型铁电体，常温下为顺电相，具有介电损耗低、漏电流小的特点。将两者形成固溶体(1-x)BiFeO 3-xSrTiO 3(x为摩尔分数，0<x<1)，通过调控x的值，并采用适当的制备方法和参数，制备的电介质薄膜的击穿场强可达3～4.5MV/cm，储能密度最高可达70.3J/cm 3，并具有70％的高储能效率。实验证明这种铁酸铋基电介质薄膜兼具较大的介电常数、较小的介电损耗、较高的击穿场强和优异的储能性能，是一种有希望应用于嵌入式电容器、静电储能元器件、脉冲功率技术等领域的材料。需要说明的是，上述针对用于高密度储能的铁酸铋基电介质薄膜所描述的特征和优点同样适用于该制备用于高密度储能的铁酸铋基电介质薄膜的方法，此处不再赘述。
在本发明的又一个方面，本发明提出了一种储能器件，根据本发明的实施例，该储能器件包括上述用于高密度储能的铁酸铋基电介质薄膜或采用上述制备用于高密度储能的铁酸铋基电介质薄膜的方法得到的用于高密度储能的铁酸铋基电介质薄膜。由此，可显著提高储能器件的储能性能。需要说明的是，上述针对用于高密度储能的铁酸铋基电介质薄膜和制备用于高密度储能的铁酸铋基电介质薄膜的方法中所描述的特征和优点同样适用于该储能器件，此处不再赘述。具体的，该储能器件可以为电介质电容器、嵌入式电容器、静电储能元器件、脉冲功率元件或基于上述器件进一步开发和组装的器件。
下面参考具体实施例，对本发明进行描述，需要说明的是，这些实施例仅仅是描述性的，而不以任何方式限制本发明。
下述实施例中样品各项性能的测试方法如下：在薄膜样品上通过直流离子溅射方法制备金属圆电极(直径为100～400μm，厚度约100nm)。介电性能测试使用美国安捷伦公司生产的E4990A阻抗分析仪，击穿场强和铁电电滞回线使用美国Radiant Tech.公司的Precision Premier II铁电测试仪测试，储能密度和效率由电滞回线计算获得。本发明的铁酸铋基电介质薄膜的结构及测试示意图如图2所示。
实施例1
将原料Fe 2O 3、SrCO 3、Bi 2O 3、TiO 2和MnO 2按(1-x)Bi 1.1Fe 0.995Mn 0.005O 3-xSrTiO 3(x＝0.30)化学式进行配料，以无水乙醇为介质球磨12小时后烘干、过筛，将制得粉末于760摄氏度预烧4小时获得铁酸铋基陶瓷粉体。向铁酸铋基陶瓷粉体中加入5％(质量百分比)浓度的PVA溶液造粒，在12MPa压片机下压制成直径约1英寸、厚度约5mm铁酸铋基陶瓷圆片。 保温排除PVA后，铁酸铋基陶瓷圆片在1100摄氏度下密封埋烧40min得到铁酸铋基陶瓷靶材。
采用脉冲激光沉积技术，利用激光轰击铁酸铋基陶瓷靶材，使其成分以化学计量比扩散到铌掺杂的钛酸锶导电单晶基底，制得外延电介质薄膜。脉冲激光沉积技术的参数包括：反应腔体本底真空度不高于5×10 -6mbar；沉积时基底温度为700摄氏度，腔体氧分压为1.3Pa，通氧气流量为1.5sccm，激光能量为1.7J/cm 2。沉积结束后，薄膜在500摄氏度、500mbar氧分压下退火30min，然后以10摄氏度/min速度降温至室温。
制得的铁酸铋基电介质薄膜厚度约450nm，图3所示为铁酸铋基电介质薄膜的断面扫描电镜图，可以发现薄膜具有良好的外延质量、表面粗糙度小，薄膜致密、均匀、无缺陷，有利于绝缘能力和储能性能的提高。图4-6分别展示了铁酸铋基电介质薄膜(x＝0.30)的介电常数、介电损耗，击穿场强和储能密度。该铁酸铋基电介质薄膜的性能达到如下指标：在1kHz下铁酸铋基电介质薄膜的介电常数和损耗分别为255和0.028，击穿场强为2.77MV/cm，储能密度达到21.8J/cm 3。
实施例2
将原料Fe 2O 3、SrCO 3、Bi 2O 3、TiO 2和MnO 2按(1-x)Bi 1.1Fe 0.995Mn 0.005O 3-xSrTiO 3(x＝0.45)化学式进行配料，以无水乙醇为介质球磨12小时后烘干、过筛，将制得粉末于760摄氏度预烧4小时获得铁酸铋基陶瓷粉体。向铁酸铋基陶瓷粉体中加入5％(质量百分比)浓度的PVA溶液造粒，在12MPa压片机下压制成直径约1英寸、厚度约5mm铁酸铋基陶瓷圆片。保温排除PVA后，铁酸铋基陶瓷圆片在1100摄氏度下密封埋烧40min得到铁酸铋基陶瓷靶材。
采用脉冲激光沉积技术，利用激光轰击铁酸铋基陶瓷靶材，使其成分以化学计量比扩散到铌掺杂的钛酸锶导电单晶基底，制得外延电介质薄膜。脉冲激光沉积技术的参数包括：反应腔体本底真空度不高于5×10 -6mbar；沉积时基底温度为700摄氏度，腔体氧分压为1.3Pa，通氧气流量为1.5sccm，激光能量为1.7J/cm 2。沉积结束后，薄膜在500摄氏度、500mbar氧分压下退火30min，然后以10摄氏度/min速度降温至室温。
制得的铁酸铋基电介质薄膜厚度约550nm，图4-6分别展示了铁酸铋基电介质薄膜(x＝0.45)的介电常数、介电损耗，击穿场强和储能密度。该铁酸铋基电介质薄膜的性能达到如下指标：在1kHz下铁酸铋基电介质薄膜的介电常数和损耗分别为300和0.029，击穿场强为3.38MV/cm，储能密度达到35.6J/cm 3。
实施例3
将原料Fe 2O 3、SrCO 3、Bi 2O 3、TiO 2和MnO 2按(1-x)Bi 1.1Fe 0.995Mn 0.005O 3-xSrTiO 3(x＝0.60)化学式进行配料，以无水乙醇为介质球磨12小时后烘干、过筛，将制得粉末于760摄氏度 预烧4小时获得铁酸铋基陶瓷粉体。向铁酸铋基陶瓷粉体中加入5％(质量百分比)浓度的PVA溶液造粒，在12MPa压片机下压制成直径约1英寸、厚度约5mm铁酸铋基陶瓷圆片。保温排除PVA后，铁酸铋基陶瓷圆片在1100摄氏度下密封埋烧40min得到铁酸铋基陶瓷靶材。
采用脉冲激光沉积技术，利用激光轰击铁酸铋基陶瓷靶材，使其成分以化学计量比扩散到铌掺杂的钛酸锶导电单晶基底，制得外延电介质薄膜。脉冲激光沉积技术的参数包括：反应腔体本底真空度不高于5×10 -6mbar；沉积时基底温度为700摄氏度，腔体氧分压为1.3Pa，通氧气流量为1.5sccm，激光能量为1.7J/cm 2。沉积结束后，薄膜在500摄氏度、500mbar氧分压下退火30min，然后以10摄氏度/min速度降温至室温。
制得的铁酸铋基电介质薄膜厚度约600nm，图4-6分别展示了铁酸铋基电介质薄膜(x＝0.60)的介电常数、介电损耗，击穿场强和储能密度。图7展示了该铁酸铋基电介质薄膜在不同电场强度下的电滞回线。该铁酸铋基电介质薄膜的性能达到如下指标：在1kHz下铁酸铋基电介质薄膜的介电常数和损耗分别为256和0.022，击穿场强为3.85MV/cm，储能密度达到70.3J/cm 3，储能效率高达70％。
实施例4
将原料Fe 2O 3、SrCO 3、Bi 2O 3、TiO 2和MnO 2按(1-x)Bi 1.1Fe 0.995Mn 0.005O 3-xSrTiO 3(x＝0.45)化学式进行配料，以无水乙醇为介质球磨12小时后烘干、过筛，将制得粉末于760摄氏度预烧4小时获得铁酸铋基陶瓷粉体。向铁酸铋基陶瓷粉体中加入5％(质量百分比)浓度的PVA溶液造粒，在12MPa压片机下压制成直径约1英寸、厚度约5mm铁酸铋基陶瓷圆片。保温排除PVA后，铁酸铋基陶瓷圆片在1100摄氏度下密封埋烧40min得到铁酸铋基陶瓷靶材。
采用脉冲激光沉积技术，利用激光轰击铁酸铋基陶瓷靶材，使其成分以化学计量比扩散到铌掺杂的钛酸锶导电单晶基底，制得外延电介质薄膜。脉冲激光沉积技术的参数包括：反应腔体本底真空度不高于5×10 -6mbar；沉积时基底温度为700摄氏度，腔体氧分压为2.6Pa，通氧气流量为2sccm，激光能量为1.4J/cm 2。沉积结束后，薄膜在500摄氏度、800mbar氧分压下退火30min，然后以10摄氏度/min速度降温至室温。
制得的铁酸铋基电介质薄膜厚度约500nm，该铁酸铋基电介质薄膜的性能达到如下指标：在测试场强为2MV/cm条件下，储能密度达到20.9J/cm 3，储能效率为52％。
实施例5
将原料Fe 2O 3、SrCO 3、Bi 2O 3、TiO 2和MnO 2按(1-x)Bi 1.1Fe 0.995Mn 0.005O 3-xSrTiO 3(x＝0.75)化学式进行配料，以无水乙醇为介质球磨12小时后烘干、过筛，将制得粉末于760摄氏度预烧4小时获得铁酸铋基陶瓷粉体。向铁酸铋基陶瓷粉体中加入5％(质量百分比)浓度的 PVA溶液造粒，在12MPa压片机下压制成直径约1英寸、厚度约5mm铁酸铋基陶瓷圆片。保温排除PVA后，铁酸铋基陶瓷圆片在1100摄氏度下密封埋烧40min得到铁酸铋基陶瓷靶材。
采用脉冲激光沉积技术，利用激光轰击铁酸铋基陶瓷靶材，使其成分以化学计量比扩散到铌掺杂的钛酸锶导电单晶基底，制得外延电介质薄膜。脉冲激光沉积技术的参数包括：反应腔体本底真空度不高于5×10 -6mbar；沉积时基底温度为700摄氏度，腔体氧分压为1.3Pa，通氧气流量为1sccm，激光能量为1.7J/cm 2。沉积结束后，薄膜在500摄氏度、500mbar氧分压下退火30min，然后以10摄氏度/min速度降温至室温。
制得的铁酸铋基电介质薄膜厚度约500nm，该铁酸铋基电介质薄膜的性能达到如下指标：在1kHz下铁酸铋基电介质薄膜的介电常数和损耗分别为187和0.020，击穿场强为4.46MV/cm，储能密度达到70.0J/cm 3，储能效率高达68％。
实施例6
将原料Fe 2O 3、SrCO 3、Bi 2O 3、TiO 2和MnO 2按(1-x)Bi 1.1Fe 0.995Mn 0.005O 3-xSrTiO 3(x＝0.60)化学式进行配料，以无水乙醇为介质球磨12小时后烘干、过筛，将制得粉末于760摄氏度预烧4小时获得铁酸铋基陶瓷粉体。向铁酸铋基陶瓷粉体中加入5％(质量百分比)浓度的PVA溶液造粒，在12MPa压片机下压制成直径约1英寸、厚度约5mm铁酸铋基陶瓷圆片。保温排除PVA后，铁酸铋基陶瓷圆片在1100摄氏度下密封埋烧40min得到铁酸铋基陶瓷靶材。
采用脉冲激光沉积技术，利用激光轰击铁酸铋基陶瓷靶材，使其成分以化学计量比扩散到铌掺杂的钛酸锶导电单晶基底，制得外延电介质薄膜。脉冲激光沉积技术的参数包括：反应腔体本底真空度不高于5×10 -6mbar；沉积时基底温度为800摄氏度，腔体氧分压为2.6Pa，通氧气流量为2sccm，激光能量为1.6J/cm 2。沉积结束后，薄膜在500摄氏度、800mbar氧分压下退火30min，然后以10摄氏度/min速度降温至室温。
制得的铁酸铋基电介质薄膜厚度约540nm，该铁酸铋基电介质薄膜的性能达到如下指标：在1kHz下铁酸铋基电介质薄膜的介电常数和损耗分别为275和0.020，击穿场强为3.6MV/cm的条件下，储能密度达到51J/cm 3，储能效率达64％。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技 术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (18)

  1. 一种用于高密度储能的铁酸铋基电介质薄膜，其特征在于，所述电介质薄膜化学成分通式为(1-x)BiFeO 3-xSrTiO 3，其中，x为摩尔分数，且0<x<1。
  2. 根据权利要求1所述的电介质薄膜，其特征在于，所述用于高密度储能的铁酸铋基电介质薄膜的厚度为150nm-2μm。
  3. 根据权利要求1或2所述的电介质薄膜，其特征在于，所述用于高密度储能的铁酸铋基电介质薄膜在Fe位进行过渡元素掺杂。
  4. 根据权利要求1-3中任一项所述的电介质薄膜，其特征在于，所述过渡元素的掺杂量为0.1wt％-2.0wt％。
  5. 一种制备权利要求1-4中任一项所述电介质薄膜的方法，其特征在于，包括：
    (1)将Bi 2O 3、Fe 2O 3、SrCO 3、TiO 2和过渡元素氧化物MeO进行混合配料，以便得到铁酸铋基原料；
    (2)将所述铁酸铋基原料和有机溶剂依次进行球磨、干燥和筛分处理，以便得到铁酸铋基粉末；
    (3)将所述铁酸铋基粉末进行预烧处理，以便得到铁酸铋基陶瓷粉体；
    (4)将所述铁酸铋基陶瓷粉体和粘合剂进行造粒和压片处理，以便得到铁酸铋基陶瓷圆片；
    (5)将所述铁酸铋基陶瓷圆片进行埋烧处理，以便得到铁酸铋基陶瓷靶材；
    (6)将所述铁酸铋基陶瓷靶材进行脉冲激光沉积处理和退火处理，以便得到用于高密度储能的铁酸铋基电介质薄膜。
  6. 根据权利要求5所述的方法，其特征在于，在步骤(1)中，所述过渡元素氧化物中的Me为选自Mn，Sc，Cr，Ni，Nb中的至少之一。
  7. 根据权利要求5或6所述的方法，其特征在于，在步骤(1)中，所述铁酸铋基原料的组成为(1-x)Bi 1.1Fe (1-y)Me yO 3xSrTiO 3，其中，0<x<1,0.001<y<0.02。
  8. 根据权利要求5-7中任一项所述的方法，其特征在于，在步骤(2)中，所述有机溶剂为选自无水乙醇、丙醇、异丙醇和乙二醇中的至少一种。
  9. 根据权利要求5-8中任一项所述的方法，其特征在于，在步骤(2)中，所述球磨处理的时间为11-13小时。
  10. 根据权利要求5-9中任一项所述的方法，其特征在于，在步骤(2)中，所述铁酸铋基粉末的粒径为100-500nm。
  11. 根据权利要求5-10中任一项所述的方法，其特征在于，在步骤(3)中，所述预烧处理的温度为750-800摄氏度，时间为3.5-4.5小时。
  12. 根据权利要求5-11中任一项所述的方法，其特征在于，在步骤(4)中，所述粘合剂为选自聚乙烯醇、聚乙二醇、正硅酸乙酯和羟丙基甲基纤维素中的至少一种。
  13. 根据权利要求5-12中任一项所述的方法，其特征在于，在步骤(4)中，所述压片处理的压力为10-14MPa。
  14. 根据权利要求5-13中任一项所述的方法，其特征在于，在步骤(4)中，所述铁酸铋基陶瓷圆片的直径为0.8-1.2英寸，厚度为3-6mm。
  15. 根据权利要求5-14中任一项所述的方法，其特征在于，在步骤(5)中，所述埋烧处理的温度为1050-1150摄氏度，时间为30-45分钟。
  16. 根据权利要求5-15中任一项所述的方法，其特征在于，在步骤(6)中，所述脉冲激光沉积处理的参数为：反应腔体本底真空度不高于5×10 -6mbar，沉积时基底温度为700-800摄氏度，腔体氧分压为1-5Pa，通氧气流量为1-10sccm，激光能量为1-2.5J/cm 2。
  17. 根据权利要求5-16中任一项所述的方法，其特征在于，在步骤(6)中，所述退火处理的温度为450-550摄氏度，氧分压为200-800mbar，退火处理的时间为15-35min。
  18. 一种储能器件，其特征在于，所述储能器件包括权利要求1-4中任一项所述的用于高密度储能的铁酸铋基电介质薄膜或采用权利要求5-17中任一项所述的方法得到的用于高密度储能的铁酸铋基电介质薄膜。
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CN107586130A (zh) * 2017-09-06 2018-01-16 天津大学 一种中温烧结低损耗钛酸钡基介质材料及其制备方法
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