CN112708160B - Polymer-based composite material for capacitor and preparation method thereof - Google Patents
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Abstract
The invention relates to a polymer matrix composite material for a capacitor and a preparation method thereof, wherein the polymer matrix composite material for the capacitor is characterized in that: the polymer-based composite material comprises an upper layer of composite material and a lower layer of composite material, wherein the composite material positioned on the upper layer is a polymer PEI/two-dimensional material composite material, and the composite material positioned on the lower layer is a polymer PEI/oxide array composite material. The polymer matrix composite material can stably work at room temperature to 150 ℃, and has high energy storage performance.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a polymer matrix composite material for a capacitor and a preparation method thereof.
Background
The high-energy-density high-voltage pulse dielectric material and the capacitor have the advantages of high power density, high charging and discharging speed, cyclic aging resistance, stable performance and the like, are important power type energy storage devices, and play a key role in high-power energy storage and pulse power systems such as power grid frequency modulation, key medical equipment, industrial lasers, new energy vehicles, advanced electromagnetic weapons and the like.
Higher demands are currently placed on the new generation of dielectric capacitors, which need to be able to operate stably in environments far above room temperature. For example, in the field of aviation and aerospace, the centralized architecture of a traditional engine monitoring system is converted into a distributed control scheme, so that the interconnection complexity can be reduced, hundreds of pounds of aircraft weight can be saved, and a plurality of electronic component devices must be placed near an engine with the temperature of 200-300 ℃; with the progress of silicon-on-insulator technology and the development of wide-band-gap semiconductor materials, the working temperature of semiconductors has been expanded to 200 ℃ or even higher; electronic capacitors used with these circuits also need to withstand the same harsh conditions in high temperature electrical appliances. In addition, some hybrid electric vehicle electronic control systems use a cooling system to reduce the ambient temperature from 120-140 ℃ to 70-80 ℃. However, the presence of a cooling system will undoubtedly increase the mass and volume of the power system, reducing the efficiency of fuel use. Therefore, the research on the pulse capacitor which can stably work in a high-temperature (not less than 150 ℃) environment and has high energy storage density is a problem which needs to be solved urgently in the high-tech field.
A polymer-based (inorganic-organic) composite is a typical capacitor energy storage material. The early stage literature shows that the microstructure (the shape, the size, the orientation and the volume fraction of the inorganic filler) of the composite energy storage material can effectively regulate and control the polarization characteristic and the energy storage capacity of the composite material. The introduction of the one-dimensional high-orientation filler in the composite material is beneficial to greatly improving the polarizability of the composite energy storage material under the condition of lower volume fraction and increasing the energy storage density and power density; and the two-dimensional filler is introduced into the polymer matrix, so that efficient conduction barriers can be established, charge movement is limited, the growth of an electronic tree in the breakdown process is hindered, the breakdown-resistant field intensity is improved, and the energy storage density and the power density are increased.
At present, most researches on high-energy-storage high-power polymer-based composite materials focus on room-temperature energy storage performance, for example, the invention patent in China, namely a polymer-based dielectric energy storage composite material with a laminated structure and a preparation method thereof, has the patent number ZL201310075684.7 (with the publication number CN 104044318B) and discloses that the laminated structure of the polymer-based dielectric energy storage composite material can obtain good high energy storage density and high breakdown field strength, but a film capacitor taking a polymer dielectric material as a main body has poor thermal stability and is difficult to stably work in a high-temperature environment. Particularly, under the action of a high electric field, the increase of the temperature can lead the internal leakage current of the polymer dielectric to be in an exponential rising trend, so that the charge-discharge efficiency and the energy storage density are sharply reduced, and the application requirement is difficult to meet.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a polymer-based composite material for a capacitor, which is stable in operation at high temperature and has high energy storage density, in view of the above-mentioned current state of the art.
The second technical problem to be solved by the invention is to provide a preparation method of a polymer-based composite material capable of realizing mass production.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a polymer matrix composite for a capacitor, characterized by: the polymer-based composite material comprises an upper layer of composite material and a lower layer of composite material, wherein the composite material positioned on the upper layer is a polymer PEI/two-dimensional material composite material, and the composite material positioned on the lower layer is a polymer PEI/oxide array composite material.
Preferably, the thickness of the upper layer composite material is 2-30 um, and the thickness of the lower layer composite material is 2-10 um.
Preferably, the two-dimensional material is one of a hexagonal boron nitride nanosheet, an alumina nanosheet, a montmorillonite nanosheet and a titanium dioxide nanosheet, and the oxide array is one of zinc oxide, barium titanate, titanium dioxide and strontium titanate.
The technical solution adopted by the present invention to solve the second technical problem is as follows: a preparation method of a polymer matrix composite material is characterized by comprising the following steps:
1) Preparing an oxide nano-array inorganic filler:
adding tetrabutyl titanate into a mixed solution of oxides containing hydrochloric acid and deionized water, wherein the volume ratio of tetrabutyl titanate to hydrochloric acid to deionized water is 1 (25-35): (25-35), stirring to form a uniform transparent solution; the clear solution was then transferred to an FTO substrate in an autoclave at temperature T 1 The reaction time t is 170-200 DEG C 1 Cooling to room temperature for 0.5-3 h, taking out the FTO substrate from the autoclave, and respectively using deionized waterAnd washing with ethanol;
2) Preparing a two-dimensional nano material inorganic filler:
stirring the nano powder for 20-25 h under the amplitude of 250-350 mA; subsequently, placed in a centrifuge tube and rotated at a rotational speed n 1 Centrifuging at 2000-4000 rpm for 20-40 min, and collecting supernatant to separate un-peeled powder; then, the supernatant is subjected to rotation at n 2 Centrifuging at 9000-11000 rpm for 20-40 min, and collecting the deposit on the wall of the centrifugal tube, wherein the deposit is two-dimensional nano-material inorganic filler;
3) Preparation of Polymer-based composite Material
First PEI is dissolved in NMP at a temperature T 5 Preparing PEI solution after stirring at 40-60 ℃; subsequently dispersing the sediment in the step 2) in NMP, and ultrasonically stirring for a time t 5 The reaction solution is slowly added into the mixture under stirring for 15-30 min to form a stable PEI/two-dimensional material suspension, and the polymer substrate is formed after bubbles are removed in a vacuum oven for 15-25 min; spin coating PEI solution on the oxide nano array inorganic filler obtained in the step 1) by adopting a spin coating method to form a one-dimensional oxide nano array composite material; finally, the PEI/two-dimensional material suspension is coated to form a one-dimensional oxide nano array composite, thereby forming the final laminated composite.
Preferably, in step 1), the volume of tetrabutyl titanate is 1ml, the volumes of hydrochloric acid and deionized water are both 30ml, and the temperature T1 is 180 ℃.
Preferably, in step 2), the stirring time t 0 Is 24h, the rotating speed n 1 Is 3000rpm and at this speed the centrifugation time t 3 Is 30min; speed n 2 10000rpm, and a centrifugation time t at the rotation speed 4 It is 30min.
In order to allow the oxide nano-array inorganic filler to be better crystallized, it is preferable that the oxide nano-array inorganic filler prepared in the step 1) is heat-treated at a heat treatment temperature T 2 At 450-750 deg.C, heat treatment time t 2 Is 1.5 to 2.5 hours. If the heat treatment temperature is too high and the heat preservation time is too long, the defects in the aspect of the capacitor performance are easily caused, thereby influencing the energy storageThe density and the thermal stability are improved; if the heat treatment temperature is too low and the heat preservation time is too short, the organic salt is not completely decomposed to form a target product; the adoption of the heat treatment conditions is beneficial to the improvement of the capacitive performance.
In order to dry the prepared two-dimensional nano-material inorganic filler, the two-dimensional nano-material inorganic filler prepared in the step 2) is preferably dried at a drying temperature T 4 The temperature is 60-80 ℃, and the drying time is 10-14 h.
Preferably, in step 3), the mass of PEI is 1g and the amount of NMP is 5ml, and after stirring at a temperature of 50 ℃ a PEI solution is prepared, the solution is stirred with ultrasound for a time t 5 For 20min, the polymer substrate was formed 20min after bubble removal. In this way, it is advantageous to disperse the deposits more uniformly.
Preferably, the polymer matrix composite prepared in step 3) is subjected to a heat treatment at a temperature T 7 At 140-220 deg.c for t 7 Is 20min to 40min. After the heat treatment is adopted for treatment, the defects in the composite material can be eliminated.
Compared with the prior art, the invention has the advantages that: the upper layer is made of the polymer PEI/two-dimensional material composite material, the lower layer is made of the polymer PEI/oxide array composite material, the lower layer is favorable for improving the dielectric constant, the upper layer is favorable for improving the breakdown field intensity, and the upper layer of the polymer PEI/two-dimensional material composite material is matched with the lower layer of the polymer PEI/oxide array composite material, so that the laminated polymer matrix composite material can stably work at room temperature to 150 ℃. The preparation method has low cost, and the thickness of the upper layer and the lower layer is controllable, so that the mass production can be realized, and the requirement can be met.
Drawings
FIG. 1 is a schematic structural view of a polymer matrix composite of example 1;
FIG. 2 is a graph of the energy storage density and efficiency of the polymer matrix composite of example 1 at 150 ℃;
FIG. 3 is a graph of the cycling stability at 150 ℃ of the polymer matrix composite of example 1.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1:
as shown in fig. 1 to 3, the present invention is the 1 st preferred embodiment.
As shown in fig. 1, the capacitor comprises an upper plate 1, a lower plate 2, and a polymer matrix composite material between the upper plate 1 and the lower plate 2. The polymer-based composite material comprises an upper layer and a lower layer, wherein the composite material on the upper layer is a polymer PEI/two-dimensional material composite material 3, the composite material on the lower layer is a polymer PEI/oxide array composite material 4, the thickness of the upper layer composite material is 2-30 um, and the thickness of the lower layer composite material is 2-10 um.
The preparation method of the polymer matrix composite material comprises the following steps:
1) Preparing oxide nano-array inorganic filler, wherein the oxide array adopts TiO 2 Nano-array:
adding tetrabutyl titanate into TiO containing hydrochloric acid and deionized water 2 Wherein, tetrabutyl titanate, hydrochloric acid and deionized water are mixed according to the volume ratio of 1:30:30, wherein the tetrabutyl titanate is 1ml, and stirring is carried out to form a uniform transparent solution; then transferring the transparent solution to an FTO substrate in an autoclave, reacting for 3h at the temperature T1 of 180 ℃, taking the FTO substrate out of the autoclave after cooling to the room temperature, and respectively washing with deionized water and ethanol to obtain TiO 2 A nano-array inorganic filler; for better crystallization, the TiO to be prepared 2 Nano array inorganic filler at heat treatment temperature T 2 Heat treatment is carried out at 500 ℃ for a time t 2 Is 2h;
the volume of the high-pressure autoclave is 100ml, and the FTO substrate adopts 4cm multiplied by 2cm; in this example, the FTO is fluorine-doped tin oxide, the PEI is polyetherimide, and the glass transition temperature of the PEI is 200-270 ℃.
2) Preparing a two-dimensional nano-material inorganic filler, wherein the two-dimensional nano-material adopts boron nitride nano-sheets (BNNS):
stirring 70-BN type powder under the amplitude of 300mA for time t 0 Is 24 hours; subsequently, placed in a centrifuge tube and rotated at a speed n 1 At a centrifugation time t of 3000rpm 3 For 30min, collecting supernatant to separate un-peeled powder; then, the supernatant is subjected to rotation at n 2 The centrifugation time t is 10000rpm 4 For 30min, collecting the deposit on the wall of the centrifuge tube, then placing the deposit BNNs in a vacuum oven at a drying temperature T 4 Drying at 70 ℃ for 12h, wherein the deposit in the step is a two-dimensional nano-material inorganic filler, namely a BNNs inorganic filler;
3) Preparation of polymer-based composite:
1g PEI was first dissolved in 5ml NMP at a temperature T 5 Preparing a PEI solution after stirring at 50 ℃; subsequently, the BNNs inorganic filler in the step 2) is dispersed in NMP, and the ultrasonic stirring time is t 5 The mixture is slowly added into the mixture under stirring for 20min to form a stable BNNs/PEI suspension, and the polymer substrate is formed after bubbles are removed in a vacuum oven for 20 min; spin coating PEI solution on the TiO of step 1) by spin coating method 2 Nano array inorganic filler to form one-dimensional TiO 2 A column nano-array composite; finally, the BNNs/PEI suspension is coated to form one-dimensional TiO 2 Nano-array composite to form the final laminated polymer matrix composite (TiO) 2 -PEI/BN-PEI); then, drying the prepared polymer-based composite material at 70 ℃ in vacuum for 2 hours to completely evaporate the solvent; finally, the prepared polymer matrix composite material is subjected to heat treatment, wherein the temperature T of the heat treatment 7 At 150 ℃ for a heat treatment time t 7 It is 30min.
The above-mentioned removal of bubbles t 6 The time is 20min, and NMP is N-methyl pyrrolidone.
As shown in FIG. 2, in order to show the variation curve of increasing energy storage density and decreasing efficiency with increasing electric field, it can be seen from FIG. 2 that the polymer-based composite material prepared by the above preparation method has excellent energy storage performance and higher efficiency at 150 ℃, wherein the energy storage density under the electric field of 400MV/m is 10.36J/cm 3 The efficiency was 82.6%.
As shown in FIG. 3, the polymer matrix composite prepared by the preparation method has good cycling stability at 150 ℃, wherein the polymer matrix composite can still work normally after being cycled for 50000 times at 150 ℃.
Example 2:
this embodiment differs from embodiment 1 described above only in that: in step 1), the transparent solution is transferred to an FTO substrate in an autoclave at a temperature T 1 At 180 ℃ for a reaction time t 1 Is 2h; in step 2) the amplitude was 250mA, in step 3) the polymer matrix composite was at a temperature T 7 At 200 ℃ for a heat treatment time t 7 It is 30min. The polymer-based composite material prepared by the embodiment can still normally work after 50000 times of circulation at 150 ℃, so that the polymer-based composite material prepared by the embodiment has good circulation stability and higher energy storage density at room temperature to 150 ℃, and the energy storage density is 10.3J/cm 3 。
Example 3:
this embodiment differs from embodiment 1 described above only in that: in step 1), the transparent solution is transferred to an FTO substrate in an autoclave at a temperature T 1 At 180 ℃ for a reaction time t 1 Is 1h; in step 2), the amplitude was 350mA.
Example 4:
this embodiment differs from embodiment 1 described above only in that: in step 1), the clear solution is transferred to an FTO substrate in an autoclave at a temperature T 1 At 180 ℃ for a reaction time t 1 It is 30min.
Example 5:
this embodiment differs from embodiment 1 described above only in that: the thickness of the composite material layer positioned on the upper layer is 2um, and the thickness of the composite material layer positioned on the lower layer is 2um; the oxide array is a barium titanate array, the two-dimensional material is an aluminum oxide nanosheet, and the parameters in the preparation method are selected differently, specifically as shown in the following table 1.
Example 6:
this embodiment differs from embodiment 1 described above only in that: the thickness of the composite material layer positioned on the upper layer is 15um, and the thickness of the composite material layer positioned on the lower layer is 10um; the oxide array is a zinc oxide array, the two-dimensional material is a montmorillonite nanosheet, and the parameters in the preparation method are selected differently, which is specifically shown in the following table 1.
Example 7:
this embodiment differs from embodiment 1 described above only in that: the thickness of the composite material layer positioned on the upper layer is 30um, and the thickness of the composite material layer positioned on the lower layer is 8um; the oxide array is made of strontium titanate, the two-dimensional material is made of titanium dioxide nanosheets, and the parameters in the preparation method are selected differently, which is shown in the following table 1.
Table 1: selection of specific parameters in the preparation methods of the above 7 examples
Claims (9)
1. A method of making a polymer matrix composite for use in a capacitor, comprising: the polymer-based composite material comprises an upper layer of composite material and a lower layer of composite material, wherein the composite material positioned on the upper layer is a polymer PEI/two-dimensional material composite material, and the composite material positioned on the lower layer is a polymer PEI/oxide array composite material, and the preparation method comprises the following steps:
1) Preparing an oxide nano-array inorganic filler:
adding tetrabutyl titanate into a mixed solution of oxides containing hydrochloric acid and deionized water, wherein the volume ratio of tetrabutyl titanate to hydrochloric acid to deionized water is 1 (25 to 35): (25 to 35), and stirring to form a uniform and transparent solution; then transferring the transparent solution to an FTO substrate in an autoclave, and reacting at the temperature T1 of 170-200 ℃ for a time T 1 Cooling to room temperature within 0.5h to 3h, taking the FTO substrate out of the high-pressure kettle, and washing with deionized water and ethanol respectively;
2) Preparing a two-dimensional nano material inorganic filler:
stirring the nano powder for 20 to 25h under the amplitude of 250 to 350mA; then placing the mixture into a centrifugal tube, centrifuging the mixture for 20 to 40min at the rotating speed n1 of 2000 to 4000rpm, and collecting supernatant to separate the powder which is not peeled off; then, centrifuging the supernatant for 20 to 40min at the rotating speed n2 of 9000 to 11000rpm, and collecting sediment on the centrifugal pipe wall, wherein the sediment is a two-dimensional nano-material inorganic filler;
3) Preparation of Polymer-based composite Material
First PEI is dissolved in NMP at a temperature T 5 Stirring at 40 to 60 ℃ to prepare a PEI solution; subsequently dispersing the sediment in the step 2) in NMP, and ultrasonically stirring for a time t 5 The reaction solution is slowly added into the mixture under stirring for 15 to 30min to form a stable PEI/two-dimensional material suspension, and air bubbles are removed in a vacuum oven for 15 to 25min to form a polymer substrate; spin coating PEI solution on the oxide nano array inorganic filler obtained in the step 1) by adopting a spin coating method to form a one-dimensional oxide nano array composite material; finally, the PEI/two-dimensional material suspension is coated on the one-dimensional oxide nano array composite material, thereby forming the final laminated composite material.
2. The method of claim 1, wherein: the thickness of the upper layer composite material is 2-30 um, and the thickness of the lower layer composite material is 2-10 um.
3. The method of claim 1, wherein: the two-dimensional material is one of hexagonal boron nitride nanosheets, alumina nanosheets, montmorillonite nanosheets and titanium dioxide nanosheets, and the oxide array is one of zinc oxide and titanium dioxide.
4. The method of claim 1, wherein: in the step 1), the volume of tetrabutyl titanate is 1ml, the volumes of hydrochloric acid and deionized water are both 30ml, and the temperature T is 1 It was 180 ℃.
5. The production method according to claim 1, characterized in that: in step 2), stirring for a time t 0 Is 24 fromh, rotational speed n 1 Is 3000rpm and at this speed the centrifugation time t 3 Is 30min; speed n 2 10000rpm, and a centrifugation time t at the rotation speed 4 It is 30min.
6. The method of claim 1, wherein: carrying out heat treatment on the oxide nano-array inorganic filler prepared in the step 1), wherein the heat treatment temperature is T 2 The temperature is 450 to 550 ℃, and the heat treatment time t 2 The reaction time is 1.5 to 2.5 hours.
7. The method of claim 1, wherein: drying the two-dimensional nano material inorganic filler prepared in the step 2) at a drying temperature T 4 The temperature is 60 to 80 ℃, and the drying time is 10 to 14h.
8. The production method according to claim 1, characterized in that: in step 3) the mass of PEI is 1g, that of NMP is 5ml and that at the temperature T 5 Preparing PEI solution after stirring at 50 ℃, and stirring for time t by ultrasonic 5 For 20min, the polymer substrate was formed 20min after bubble removal.
9. The method of claim 1, wherein: carrying out heat treatment on the polymer matrix composite material prepared in the step 3), wherein the heat treatment temperature T is 7 The temperature is 140 to 220 ℃, and the heat preservation time t is 7 20min to 40min.
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CN110713618A (en) * | 2019-09-26 | 2020-01-21 | 南方科技大学 | Polymer-based composite dielectric material, preparation method thereof and energy storage device |
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