CN113690050B - Layered composite relaxation ferroelectric material capable of simultaneously improving energy storage density and energy storage efficiency and preparation method thereof - Google Patents
Layered composite relaxation ferroelectric material capable of simultaneously improving energy storage density and energy storage efficiency and preparation method thereof Download PDFInfo
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Abstract
The application discloses a layered composite relaxation ferroelectric material capable of simultaneously improving energy storage density and energy storage efficiency and a preparation method thereof. The layered composite relaxor ferroelectric material comprises a rigid substrate, a lower electrode layer formed on the rigid substrate, a layered composite relaxor ferroelectric layer formed on the lower electrode layer, and an upper electrode layer formed on the layered composite relaxor ferroelectric layer, wherein the layered composite relaxor ferroelectric layer is a multilayer structure film with relaxor ferroelectricity, and the multilayer structure film comprises a lower layer and an upper layer which are sequentially and repeatedly and multi-periodically superposed and grown on the lower electrode layer; the preparation method comprises the following steps: selecting an STO substrate, generating an SRO layer on the STO substrate, generating a plurality of BTO-STO layers on the SRO layer to form a layered composite relaxor ferroelectric layer, and generating the SRO layer on the layered composite relaxor ferroelectric layer to obtain the layered composite relaxor ferroelectric material. The layered composite relaxor ferroelectric material has excellent energy storage density and energy storage efficiency.
Description
Technical Field
The present application relates to the field of relaxor ferroelectric energy storage, and more particularly, to a layered composite relaxor ferroelectric material capable of simultaneously improving energy storage density and energy storage efficiency, and a method for preparing the same.
Background
Dielectric capacitors are used as energy storage cores of energy storage devices, have the advantages of high power density, high charge and discharge speed, long cycle life and the like, and are widely focused and researched, but the development of the dielectric capacitors is limited by the defect of low energy density, so that research begins to improve the energy density of the dielectric capacitors in various different modes.
Currently, the dielectric energy storage materials of dielectric capacitors are mainly classified into four types, namely linear dielectric materials, ferroelectric materials, relaxor ferroelectric materials and antiferroelectric materials. Wherein the linear dielectric material has low energy storage density due to low breakdown field strength; ferroelectric materials also result in low energy storage efficiency due to large energy storage losses and high remnant polarization; the antiferroelectric material also has the phenomenon of reduced energy storage efficiency due to large energy storage loss; the relaxation ferroelectric material has higher breakdown field strength and lower remnant polarization intensity value, thus having higher energy storage density and energy storage efficiency.
The current research has reached the bottleneck period for improving the energy storage performance of the relaxation ferroelectric material, so the research direction starts to be towards different novel structures to improve the energy storage performance of the relaxation ferroelectric material, including methods of two-phase solid solution, interface engineering technology and the like. The interface engineering technology is applied to the relaxation ferroelectric material all the time due to low preparation cost, simple preparation flow and obvious improvement of energy storage performance.
Therefore, the relaxation ferroelectric capacitor with higher energy storage density and energy storage efficiency is researched and prepared by utilizing the interface engineering technology, and has great significance for the development and research of future energy storage equipment.
Disclosure of Invention
In order to solve the problem that the existing relaxation ferroelectric capacitor is poor in energy storage density and energy storage efficiency, the application provides a layered composite relaxation ferroelectric material capable of improving the energy storage density and the energy storage efficiency at the same time and a preparation method thereof.
In a first aspect, the present application provides a layered composite relaxor ferroelectric material capable of simultaneously improving energy storage density and energy storage efficiency, which adopts the following technical scheme:
a layered composite relaxor ferroelectric material capable of simultaneously improving energy storage density and energy storage efficiency comprises a rigid substrate, a lower electrode layer formed on the rigid substrate, a layered composite relaxor ferroelectric layer formed on the lower electrode layer, and an upper electrode layer formed on the layered composite relaxor ferroelectric layer;
the layered composite relaxor ferroelectric layer is a multilayer structure film with relaxor ferroelectricity based on the growth of the lower electrode layer, and the multilayer structure film comprises a lower layer and an upper layer which are sequentially overlapped and grown on the lower electrode layer, and the lower layer and the upper layer are repeatedly overlapped in multiple periods.
By adopting the technical scheme, the prepared layered composite relaxor ferroelectric material has the structure of a relaxor ferroelectric film crystal, has the advantages of higher energy storage density, higher energy storage efficiency, wider-range working temperature, higher saturated polarization intensity value and lower residual polarization intensity value, and also solves the problem that the increase of the polarization intensity and the reduction of the energy storage consumption cannot be realized at the same time.
Preferably, the rigid substrate is SrTiO 3 (STO) substrate having a crystal plane orientation of [100]]。
Preferably, the lower electrode layer is SrRuO grown based on the rigid substrate 3 (SRO) layer.
Preferably, the upper electrode layer is SrRuO based on the growth of the layered composite relaxor ferroelectric layer 3 (SRO) layer.
Preferably, the constituent elements of the lower layer include Ba and Ti, and the constituent elements of the upper layer include Sr and Ti.
Preferably, the multilayer structure film is BaTiO 3 （BTO）-SrTiO 3 (STO) bilayer structure.
Preferably, the total thickness of the upper layer in the layered composite relaxor ferroelectric layer is smaller than the total thickness of the upper electrode layer and the lower electrode layer, the lower layer of the layered composite relaxor ferroelectric layer is the main layer of the layered composite relaxor ferroelectric layer, and the total thickness of the lower layer accounts for 80% -85% of the total thickness of the layered composite relaxor ferroelectric layer.
By adopting the technical scheme, the total thickness of the lower layer is controlled to be 80% -85% of the total thickness of the layered composite relaxation ferroelectric layer, and the prepared material has better energy storage density and energy storage efficiency.
Preferably, the thicknesses of the lower electrode layer and the upper electrode layer are 20-40 nm, the total thickness of the upper layer in the layered composite relaxor ferroelectric layer is 35-60 nm, the total thickness of the lower layer in the layered composite relaxor ferroelectric layer is 200-260 nm, and the thickness of the layered composite relaxor ferroelectric layer is 280-320 nm.
Preferably, the thicknesses of the lower electrode layer and the upper electrode layer are both 30-35 nm, the total thickness of the upper layer in the layered composite relaxor ferroelectric layer is 55-60 nm, the total thickness of the lower layer in the layered composite relaxor ferroelectric layer is 235-250 nm, and the thickness of the layered composite relaxor ferroelectric layer is 290-310 nm.
In a second aspect, the present application provides a method for preparing a layered composite relaxor ferroelectric material capable of simultaneously improving energy storage density and energy storage efficiency, which adopts the following technical scheme:
a preparation method of a layered composite relaxor ferroelectric material capable of simultaneously improving energy storage density and energy storage efficiency comprises the following steps:
(1) Selecting a rigid substrate with specific crystal face orientation;
(2) Generating a lower electrode layer on the selected rigid substrate with specific crystal face orientation;
(3) Generating a layered composite relaxor ferroelectric layer with relaxor ferroelectricity on the lower electrode layer, wherein the layered composite relaxor ferroelectric layer is formed by repeatedly and repeatedly superposing multiple periods of a multi-layer structure film with a lower layer and an upper layer;
(4) And generating an upper electrode layer on the layered composite relaxor ferroelectric layer to obtain the layered composite relaxor ferroelectric material.
The P-E ring of the layered composite relaxor ferroelectric material prepared by the preparation method is more slender, and the remnant polarization intensity is reduced, so that the energy storage efficiency is improved.
Preferably, the method comprises the following steps:
(1) Selecting STO substrate with crystal face orientation of [100] as rigid substrate;
(2) Generating an SRO layer as a lower electrode layer on the STO rigid substrate;
(3) Repeatedly generating a plurality of BTO-STO layers on the SRO lower electrode layer in multiple periods, and stacking the plurality of BTO-STO layers to form a layered composite relaxor ferroelectric layer;
(4) And generating an SRO layer serving as an upper electrode layer on the layered composite relaxor ferroelectric layer to obtain the layered composite relaxor ferroelectric material.
Preferably, the lower electrode layer is generated in the step (2), the layered composite relaxor ferroelectric layer is generated in the step (3), and the upper electrode layer is generated in the step (4) by adopting a pulse laser deposition method.
Preferably, step (3) comprises the steps of:
A. respectively placing a BTO target and a STO target on two adjacent target positions;
B. performing bonding treatment on the STO substrate in the step (1) and placing the STO substrate right above a main target in a growth cavity of a pulse laser deposition system, wherein the distance between the STO substrate and the target is controlled to be-10 cm;
C. switching the BTO target position to a main target position, and starting a laser to bombard the BTO target material 120-1200 a;
D. rapidly switching the STO target position to a main target position, and starting a laser to bombard the STO target material for 20-200 times;
E. and (3) repeating the process of the steps C-D for 10-100 times to obtain the BTO-STO layered composite relaxor ferroelectric material with the repetition period N of 10-100.
Preferably, the deposition parameters of the lower electrode layer in the step (2) and the upper electrode layer in the step (4) are controlled as follows: the vacuum degree of deposition is less than or equal to 1 multiplied by 10 -7 Pa, the deposition temperature is 680-720 ℃, the oxygen partial pressure is 70-90 mTorr, the laser energy is 340-360 mJ, the pulse laser frequency is 1-10 Hz, the deposition temperature rate is 20-30 ℃/min, the laser focal length is 0-30 mm, and the deposition rate is 2-5 nm/min.
Preferably, the deposition vacuum degree of the layer-shaped composite relaxation ferroelectric layer in the step (3) is less than or equal to 1 multiplied by 10 -7 Pa, the deposition temperature is 720-760 ℃, the oxygen partial pressure is 5-20 mTorr, the laser energy is 360-400 mJ, the pulse laser frequency is 1-10 Hz, the deposition temperature rate is 20-30 ℃/min, the laser focal length is-30-0 mm, and the deposition rate is 2-5 nm/min.
By controlling the deposition parameters of the lower electrode layer, the upper electrode layer and the layered composite relaxor ferroelectric layer, the prepared layered composite relaxor ferroelectric material not only has better energy storage density and energy storage efficiency, but also can obtain better internal structure and compactness.
Preferably, the prepared layered composite relaxor ferroelectric material is subjected to a cooling post-treatment comprising the steps of:
a. placing the prepared layered composite relaxor ferroelectric material for 20-40 min under the conditions that the temperature is 720-760 ℃ and the oxygen partial pressure is 5-20 mTorr;
b. and slowly cooling the layered composite relaxor ferroelectric material to room temperature at a cooling speed of 10-30 ℃/min.
The temperature reduction speed is controlled in the original deposition oxygen partial pressure atmosphere, so that the energy storage density and the energy storage efficiency of the prepared layered composite relaxation ferroelectric material are improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the layered composite relaxor ferroelectric material prepared by the application has the structure of a relaxor ferroelectric thin film crystal so as to have perovskite oxide SrRuO 3 The film is used as the upper and lower electrodes, and the core lower layer BaTiO is used as the premise 3 SrTiO of upper layer 3 The composite relaxor ferroelectric film as the dielectric layer has similar lattice constant and excellent lattice matching degree, and can grow high quality relaxor ferroelectric film and is favorable to raising the energy storing performance of the capacitor.
2. The layered composite relaxor ferroelectric material prepared by the method has lower leakage current density, lower residual polarization intensity and higher saturation polarization intensity, and the P-E ring is more slender and is more beneficial to energy storage of the capacitor.
3. The layered composite relaxor ferroelectric material prepared by the method has the advantages of higher energy storage density, higher energy storage efficiency, wider-range working temperature, higher saturated polarization intensity value and lower residual polarization intensity value, and when the repetition period of BTO-STO is 50, the energy storage density of the layered composite relaxor ferroelectric material can reach 22.99J/cm 3 The energy storage efficiency can reach 79.61%, and the energy storage performance of the capacitor prepared from the BTO-STO layered composite relaxation ferroelectric materials with different repetition periods is better than that of a pure BTO ferroelectric capacitor.
Drawings
FIG. 1 is a schematic cross-sectional view of a multi-layered composite relaxor ferroelectric material in accordance with an embodiment of the present application;
FIG. 2 is a flow chart of the preparation of a multi-layered composite relaxor ferroelectric material in accordance with an embodiment of the present application;
FIG. 3 is an XRD pattern of a layered composite relaxor ferroelectric material prepared in example 2 and comparative example of the present application;
FIG. 4 is a TEM image of a layered composite relaxor ferroelectric material prepared in example 2 of the present application;
FIG. 5 is a P-V diagram of layered composite relaxor ferroelectric materials prepared in example 2 and comparative examples of the present application;
FIG. 6 is a J-V diagram of a layered composite relaxor ferroelectric material prepared in example 2 and comparative example of the present application;
FIG. 7 is a C-V diagram of a layered composite relaxor ferroelectric material prepared in example 2 of the present application;
FIG. 8 is a graph showing the recoverable energy storage density (W) of the layered composite relaxor ferroelectric materials prepared in example 2 and comparative example of the present application rec ) A figure;
fig. 9 is a graph of energy storage efficiency (η) of layered composite relaxor ferroelectric materials prepared in example 2 and comparative examples of the present application.
Detailed Description
Dielectric capacitors are used as energy storage cores of energy storage devices, and dielectric energy storage materials thereof are mainly divided into four types, namely linear dielectric materials, ferroelectric materials, relaxor ferroelectric materials and antiferroelectric materials. Wherein the relaxed ferroelectric material has higher breakdown field strength, lower remnant polarization value, and thus higher energy storage density and energy storage efficiency. The current research has reached the bottleneck period for improving the energy storage performance of the relaxor ferroelectric material, so the research direction starts to be towards different novel structures to improve the energy storage performance of the relaxor ferroelectric material, wherein the interface engineering technology is obviously and always applied to the relaxor ferroelectric material due to low preparation cost, simple preparation flow and improved energy storage performance. Through a great deal of research, the application researches a layered composite relaxation ferroelectric material with higher energy storage density and energy storage efficiency, and has the advantages of higher energy storage density, higher energy storage efficiency, wider-range working temperature, higher saturated polarization intensity value and lower residual polarization intensity value.
In order to facilitate understanding of the technical solutions of the present application, the present application will be further described in detail below with reference to the drawings and examples, but not as a protection scope defined by the present application.
Examples
Example 1
As shown in fig. 1, a layered composite relaxor ferroelectric material capable of simultaneously improving energy storage density and energy storage efficiency, comprising: the ferroelectric device comprises a rigid substrate, a lower electrode layer formed on the rigid substrate, a layered composite relaxor ferroelectric layer formed on the lower electrode layer, and an upper electrode layer formed on the layered composite relaxor ferroelectric layer.
The layered composite relaxor ferroelectric layer is a multilayer structure film with relaxor ferroelectricity based on the growth of the lower electrode layer, the multilayer structure film comprises a lower layer and an upper layer which are sequentially stacked and grown on the lower electrode layer, and the multilayer structure film is formed by repeatedly stacking the lower layer and the upper layer for multiple periods, wherein in the embodiment, the repetition period is n=10.
As shown in fig. 2, the preparation method of the layered composite relaxor ferroelectric material comprises the following steps:
(1) Selecting a rigid substrate, wherein the rigid substrate is SrTiO 3 (STO) substrate having a crystal plane orientation of [100]]。
(2) Deposition of SrRuO onto STO rigid substrates using pulsed laser deposition systems 3 The (SRO) layer is used as a lower electrode layer, and the thickness of the lower electrode layer formed by deposition is 31nm; controlling vacuum degree of deposition cavity to be less than or equal to 1 multiplied by 10 in deposition process -7 Pa, deposition temperature of 690 ℃, oxygen partial pressure of 80mTorr, laser energy of 350mJ, pulse laser frequency of 9.9Hz, deposition temperature rate of 25 ℃/min, laser focal length of 20mm, and deposition rate of 3nm/min.
(3) Deposition of BaTiO with a layered structure with fringing ferroelectricity on a SRO bottom electrode layer using a pulsed laser deposition system 3 （BTO）-SrTiO 3 (STO) film as layered composite relaxor ferroelectric layer, and layered composite relaxor formed by depositionThe thickness of the ferroelectric layer is 300nm, wherein the thickness of the BTO layer is 240nm, the thickness of the STO layer is 60nm, and the specific steps are as follows:
A. respectively placing a BTO target and a STO target on two adjacent target positions;
B. performing bonding treatment on the STO substrate in the step (1), placing the STO substrate right above a main target position in a growth cavity of a pulse laser deposition system, controlling the distance between the STO substrate and the target to be 0cm, and adjusting the vacuum degree of the deposition cavity to be less than or equal to 1 multiplied by 10 -7 Pa, the deposition temperature is 730 ℃, the oxygen partial pressure is 5mTorr, the laser energy is 380mJ, the pulse laser frequency is 9.9Hz, the deposition temperature rate is 25 ℃/min, the laser focal length is-20 mm, and the deposition rate is 3nm/min;
the specific steps of the bonding treatment are as follows:
b1, cleaning the surface of the STO substrate, dipping a small amount of alcohol solution by using a dust-free cotton swab to wipe the surface of the STO substrate, and repeating for 3 times until the surface of the STO substrate has no other impurities;
b2, coating the surface of the heating backboard with a conductive silver paste solution, and bonding the cleaned STO substrate on the heating backboard;
b3, placing the STO substrate and the heating backboard in a growth cavity of the pulse laser deposition system;
C. switching the BTO target position to a main target position, and starting a laser to bombard the BTO target material by 1200 times of fixed shots;
D. rapidly switching the STO target position to a main target position, and starting a laser to bombard the STO target material for 200 times;
E. and (3) repeating the process of the steps C-D for 10 times to obtain the BTO-STO layered composite relaxor ferroelectric layer with the repetition period of N=10.
(4) SrRuO is deposited and formed on the layered composite relaxor ferroelectric layer by using a pulse laser deposition system 3 The (SRO) layer is used as an upper electrode layer, and the thickness of the upper electrode layer formed by deposition is 31nm, so that the layered composite relaxation ferroelectric material is prepared; controlling vacuum degree of deposition cavity to be less than or equal to 1 multiplied by 10 in deposition process -7 Pa, deposition temperature of 690 ℃, oxygen partial pressure of 80mTorr, laser energy of 350mJ, pulse laser frequency of 9.9Hz, deposition temperature rate of 25 ℃/min, laser focusThe distance was 20mm and the deposition rate was 3nm/min.
(5) Cooling post-treatment is carried out on the prepared lamellar composite relaxor ferroelectric material, and the method comprises the following steps:
a. placing the prepared layered composite relaxor ferroelectric material for 40min under the conditions that the temperature is 730 ℃ and the oxygen partial pressure is 5 mTorr;
b. slowly cooling the layered composite relaxor ferroelectric material to room temperature at a cooling rate of 20 ℃/min to obtain a BTO-STO layered composite relaxor ferroelectric material finished product.
Example 2
The difference from example 1 is that the number of fixed shots of bombarded BTO targets in step C is 240, the number of fixed shots of bombarded STO targets in step D is 40, and the process of steps C to D is repeated 50 times to obtain the BTO-STO layered composite relaxor ferroelectric material with a repetition period of n=50.
Comparative example
The difference from example 1 is that the BTO film having ferroelectricity is deposited on the SRO lower electrode layer in step (3) directly as a layered composite relaxor ferroelectric layer with a thickness of 300nm.
As is evident from the XRD pattern, there are BTO phases preferentially grown along (100), (200) and (300) and bottom electrode layer SRO phases preferentially grown along (100), (200) and (300) in addition to the STO substrate peaks (100), (200) and (300), demonstrating the formation of single crystals of the BTO-STO layer.
As shown in fig. 4, the thickness of the SRO lower electrode layer and the thickness of the layered composite relaxor ferroelectric layer were 31nm and 300nm, respectively, as can be seen from the high-resolution TEM image of fig. 4a, whereas the BTO layer and the STO layer were sequentially deposited layered structures, as can be seen from the low-resolution TEM image of fig. 4b, and have very obvious boundaries, demonstrating that the prepared layered composite relaxor ferroelectric material is grown in layers.
As shown in fig. 5, the ferroelectric hysteresis loop of the layered composite relaxor ferroelectric material of the BTO-STO layer at the repetition period n=50 is more elongated than that of the pure BTO ferroelectric material, and although the saturation polarization value is slightly reduced, the P-E ring becomes more elongated and the influence of the decrease in the remnant polarization on the improvement of the energy storage performance is greater, so that the structure of the layered composite relaxor ferroelectric material can be more advantageous for improving the energy storage performance of the capacitor.
As shown in fig. 6, the leakage current density of the layered composite relaxor ferroelectric material of the BTO-STO layer at the repetition period n=50 is lower than that of the pure BTO ferroelectric material, and the lower leakage current density is easier to obtain better energy storage performance, so the structure of the layered composite relaxor ferroelectric material can be more beneficial to improving the energy storage performance of the capacitor.
As shown in fig. 7, the C-V diagram of the composite relaxor ferroelectric material of the BTO-STO layer at the repetition period of n=50 is shown, and the C-V diagram is the capacitance values at the frequencies of 50 kHz, 100 kHz, 200 kHz, 500 kHz and 1 MHz, respectively, and the CV loop area at each corresponding frequency represents the magnitude of the remnant polarization at different frequencies, and the CV loop can be more stable at higher frequencies, so that the layered composite relaxor ferroelectric material can be kept stable at higher frequencies, which is beneficial for the capacitor to be applied in various different condition environments.
As shown in fig. 8, the energy storage density of the composite relaxor ferroelectric material of the BTO-STO layer at the repetition period of n=50 can reach 22.99J/cm 3 Compared with pure BTO ferroelectric material, the energy storage density of the material is 19.89J/cm 3 The improvement is 15.59 percent.
As shown in fig. 9, the energy storage efficiency of the BTO-STO layer in the composite relaxor ferroelectric material at the repetition period of n=50 can reach 79.61%, which is 48.91% higher than that of the pure BTO ferroelectric film.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (7)
1. A layered composite relaxor ferroelectric material capable of simultaneously increasing energy storage density and energy storage efficiency, comprising: a rigid substrate, a lower electrode layer formed on the rigid substrate, a layered composite relaxor ferroelectric layer formed on the lower electrode layer, and an upper electrode layer formed on the layered composite relaxor ferroelectric layer;
the layered composite relaxor ferroelectric layer is a multilayer structure film with relaxor ferroelectricity based on the growth of the lower electrode layer, and the multilayer structure film comprises a lower layer and an upper layer which are sequentially overlapped and grown on the lower electrode layer, wherein the lower layer and the upper layer are repeatedly overlapped in multiple periods;
the rigid substrate is SrTiO 3 (STO) substrate having a crystal plane orientation of [100]]；
The lower electrode layer is SrRuO grown based on the rigid substrate 3 (SRO) layer;
the upper electrode layer is SrRuO based on the growth of the layered composite relaxor ferroelectric layer 3 (SRO) layer;
the multilayer structure film is BaTiO 3 （BTO）-SrTiO 3 (STO) bilayer structure;
the preparation method comprises the following steps:
(1) Selecting STO substrate with crystal face orientation of [100] as rigid substrate;
(2) Generating an SRO layer as a lower electrode layer on the STO rigid substrate;
(3) Repeatedly generating a plurality of BTO-STO layers on the SRO lower electrode layer in multiple periods, and stacking the plurality of BTO-STO layers to form a layered composite relaxor ferroelectric layer;
(4) Generating an SRO layer as an upper electrode layer on the layered composite relaxor ferroelectric layer to obtain a layered composite relaxor ferroelectric material;
the lower electrode layer is generated in the step (2), the layered composite relaxor ferroelectric layer is generated in the step (3), and the upper electrode layer is generated in the step (4) by adopting a pulse laser deposition method;
step (3) comprises the following steps:
A. respectively placing a BTO target and a STO target on two adjacent target positions;
B. performing bonding treatment on the STO substrate in the step (1) and placing the STO substrate right above a main target in a growth cavity of a pulse laser deposition system, wherein the distance between the STO substrate and the target is controlled to be-10 cm;
C. switching the BTO target position to a main target position, and starting a laser to bombard the BTO target material 120-1200 a;
D. rapidly switching the STO target position to a main target position, and starting a laser to bombard the STO target material for 20-200 times;
E. and (3) repeating the process of the steps C-D for 10-100 times to obtain the BTO-STO layered composite relaxor ferroelectric material with the repetition period N of 10-100.
2. The layered composite relaxor ferroelectric material capable of simultaneously increasing energy storage density and energy storage efficiency as claimed in claim 1, wherein: the total thickness of the upper layer in the layered composite relaxor ferroelectric layer is smaller than the total thickness of the upper electrode layer and the lower electrode layer, the lower layer of the layered composite relaxor ferroelectric layer is the main layer of the layered composite relaxor ferroelectric layer, and the total thickness of the lower layer accounts for 80% -85% of the total thickness of the layered composite relaxor ferroelectric layer.
3. The layered composite relaxor ferroelectric material capable of simultaneously increasing energy storage density and energy storage efficiency as claimed in claim 2, wherein: the thicknesses of the lower electrode layer and the upper electrode layer are 20-40 nm, the total thickness of the upper layer in the layered composite relaxor ferroelectric layer is 35-60 nm, the total thickness of the lower layer in the layered composite relaxor ferroelectric layer is 200-260 nm, and the thickness of the layered composite relaxor ferroelectric layer is 280-320 nm.
4. A layered composite relaxor ferroelectric material as claimed in claim 3, wherein the energy storage density and the energy storage efficiency are both improved, wherein: the thicknesses of the lower electrode layer and the upper electrode layer are 30-35 nm, the total thickness of the upper layer in the layered composite relaxor ferroelectric layer is 55-60 nm, the total thickness of the lower layer in the layered composite relaxor ferroelectric layer is 235-250 nm, and the thickness of the layered composite relaxor ferroelectric layer is 290-310 nm.
5. The method for preparing the layered composite relaxor ferroelectric material capable of simultaneously improving the energy storage density and the energy storage efficiency according to claim 2, wherein the method comprises the steps of: a lower electrode layer in the step (2) and the step (4)The deposition parameters of the upper electrode layer are controlled as follows: the vacuum degree of deposition is less than or equal to 1 multiplied by 10 -7 Pa, the deposition temperature is 680-720 ℃, the oxygen partial pressure is 70-90 mTorr, the laser energy is 340-360 mJ, the pulse laser frequency is 1-10 Hz, the deposition temperature rate is 20-30 ℃/min, the laser focal length is 0-30 mm, and the deposition rate is 2-5 nm/min.
6. The method for preparing the layered composite relaxor ferroelectric material capable of simultaneously improving energy storage density and energy storage efficiency as claimed in claim 1, wherein the method comprises the steps of: the deposition vacuum degree of the layered composite relaxor ferroelectric layer in the step (3) is less than or equal to 1 multiplied by 10 -7 Pa, the deposition temperature is 720-760 ℃, the oxygen partial pressure is 5-20 mTorr, the laser energy is 360-400 mJ, the pulse laser frequency is 1-10 Hz, the deposition temperature rate is 20-30 ℃/min, the laser focal length is-30-0 mm, and the deposition rate is 2-5 nm/min.
7. The method for preparing the layered composite relaxor ferroelectric material capable of simultaneously improving energy storage density and energy storage efficiency as claimed in claim 1, wherein the method comprises the steps of: cooling post-treatment is carried out on the prepared lamellar composite relaxor ferroelectric material, and the method comprises the following steps:
a. placing the prepared layered composite relaxor ferroelectric material for 20-40 min under the conditions that the temperature is 720-760 ℃ and the oxygen partial pressure is 5-20 mTorr;
b. and slowly cooling the layered composite relaxor ferroelectric material to room temperature at a cooling speed of 10-30 ℃/min.
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| CN115852311A (en) * | 2022-11-03 | 2023-03-28 | 湘潭大学 | AB two-phase gradient film, large-area gradient film material and preparation method |
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