CN111180219B - Based on PI/ZrO2Preparation method of nanofiber carbon aerogel flexible supercapacitor - Google Patents
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Abstract
The invention provides a method based on PI/ZrO2A preparation method of a nanofiber carbon aerogel flexible supercapacitor belongs to the field of flexible supercapacitors. The preparation method comprises the following steps: firstly, preparing nascent fibers of polyimide nanofibers and zirconia nanofibers by using an electrostatic spinning technology, shearing the prepared nanofiber membrane into blocks, crushing and dispersing the two nanofibers into a uniform single-layer graphene oxide aqueous solution by using a high-speed homogenizer according to a certain proportion, and preparing the polyimide/zirconia-based composite fiber carbon aerogel by using a freeze drying technology, a thermal imidization technology and a high-temperature carbonization technology. The composite carbon aerogel prepared by the invention is formed by assembling the nano fibers and the support body, has uniform pore diameter distribution, large specific surface area, high strength, small density, excellent mechanical property, compression resilience and good conductivity, and has good application prospect in the field of flexible supercapacitor electrode materials.
Description
Technical Field
The invention belongs to flexibilityThe field of wearable super capacitors relates to a capacitor based on PI/ZrO2A preparation method of a nanofiber carbon aerogel flexible supercapacitor.
Background
The carbon aerogel is a three-dimensional light and porous carbon material, has the characteristics of large specific surface area, high aperture ratio, excellent ultralow density and conductivity and the like, can be applied to the fields of adsorbents, catalyst carriers, fireproof materials, electrode materials and the like, has excellent application prospects in the aspect of energy storage, and is one of the research hotspots in recent years. The types of carbon aerogels at present mainly comprise biochar, carbon nanotubes, graphene and carbon nanofiber-based carbon aerogels. The biological carbon aerogel is limited by the structure of the raw material, and the microstructure of the material is not easy to regulate and control; the preparation of carbon nanotubes or graphene-based carbon aerogels requires high bulk density of raw materials, a corresponding increase in material cost, and general mechanical properties. In contrast, the carbon nanofiber is simple to prepare, flexible in structure regulation and high in strength, and is an excellent carbon aerogel basic construction unit.
And the electrospinning technique is the most commonly used technique for preparing nanofibers. Therefore, the polyamic acid nanofiber and the zirconia nascent fiber are used as precursors, and the carbon aerogel material consisting of the one-dimensional carbon nanofiber and the two-dimensional sheet carbon is successfully prepared through the technical processes of high-speed homogenization, freeze drying, thermal imidization, carbonization and the like. The composite carbon aerogel can be used as the most potential material in energy storage and conversion devices due to high specific surface area, high porosity, excellent mechanical properties and good ion transmission performance. The flexible super capacitor with excellent electrochemical performance can be prepared by using the graphene oxide as an electrode material.
Disclosure of Invention
Aiming at the technical problems of low charging and discharging speed, small capacity and poor flexibility in the prior art, the invention provides a PI/ZrO based material2The preparation method of the nanofiber carbon aerogel flexible supercapacitor is simple and convenient in the whole preparation process, easy to operate, low in cost and environment-friendly. The composite carbon aerogel prepared by the invention is formed by assembling nano-fibers and a support body, and the material has uniform pore size distributionThe flexible super capacitor electrode material has the advantages of large specific surface area, high strength, small density, excellent mechanical property, compression resilience and good conductivity, and has good application prospect in the field of flexible super capacitor electrode materials.
In order to solve the technical problems, the invention adopts the following technical scheme:
based on PI/ZrO2The preparation method of the nanofiber carbon aerogel flexible supercapacitor comprises the following steps: spinning a nanofiber membrane by an electrostatic spinning technology, smashing the nanofiber membrane into a dispersion liquid of graphene oxide to form a uniform and stable nanofiber suspension, freezing the suspension into a solid by liquid nitrogen or a refrigerator, preparing a nanofiber aerogel by a freeze-drying technology, carbonizing the aerogel at a high temperature to form a carbon nanofiber aerogel, and finally assembling the carbon nanofiber aerogel with a gel electrolyte to obtain the supercapacitor.
The method comprises the following specific steps:
(1) preparing polyamide acid (PAA) spinning solution and zirconia nascent fiber spinning solution, and preparing a PAA nanofiber membrane and a zirconia nascent fiber membrane by an electrostatic spinning method, wherein the diameter of the nanofiber is 100-600 nm;
(2) cutting the PAA nanofiber membrane and the zirconia nascent fiber membrane obtained in the step (1) into small pieces, putting the small pieces into GO dispersion liquid according to the mass fraction of 0.6-1.5%, and smashing the nanofiber membrane by using a high-speed homogenizer to form stable and uniform nanofiber blending dispersion liquid;
(3) pouring the nanofiber blending dispersion liquid obtained in the step (2) into a mold, freezing the nanofiber blending dispersion liquid into a solid by using liquid nitrogen or a refrigerator, and placing the solid on a freeze dryer for drying for 20-45 hours to obtain the composite nanofiber aerogel;
(4) putting the composite nanofiber aerogel obtained in the step (3) into a vacuum atmosphere box-type furnace, and setting a program to perform gradient temperature rise, wherein the temperature rise process comprises two processes: thermal imidization, high-temperature carbonization and formation of zirconia nanofibers of polyamic acid; obtaining the porous composite aerogel;
(5) coating the gel electrolyte on one surface of the porous composite aerogel carbonized at high temperature, standing for 30 DEG CAfter min, coating the gel electrolyte on the electrode materials, repeating for 2-5 times, superposing the surfaces of the two electrode materials coated with the gel electrolyte to form a sandwich structure, and assembling to obtain the polyimide/zirconium oxide (PI/ZrO/PI/ZrO) -based electrode material2) A flexible supercapacitor of carbon aerogel.
Further, the preparation method of the polyamic acid (PAA) spinning solution in the step (1) is as follows: adding pyromellitic dianhydride (PMDA) and 4-4' -diaminodiphenyl ether (ODA) into N, N-dimethylacetamide according to the mass ratio of ODA: PMDA =1:1.02, and dissolving for 3-10 h at 0 ℃ in an ice bath to obtain a polyamic acid (PAA) spinning solution with the mass concentration of 21% -25%.
Further, the preparation method of the zirconia primary fiber spinning solution in the step (1) is as follows: mixing n-basic zirconium Carbonate (CH)2O7Zr2): n acetic acid (CH)3COOH): n methanol (CH)3OH) =1:1:10, adding yttrium nitrate (Y) after uniformly mixing2O3）（CH2O7Zr2：Y2O3And = 6%) are heated and stirred in a water bath (the temperature is about 30-40 ℃ and the rotating speed is 500 r/min).
Further, the electrostatic spinning process parameters in the step (1) are as follows: the voltage is 15-30 kV, the used spinning container is a 10 mL plastic injector with a pinhole diameter of 0.5 mm, the flow rate is 0.06-0.5 mm/min, the receiving distance is 10-20 cm, the spinning temperature is 20-35 ℃, and the humidity is 25-50 RH%.
Further, the mass ratio of the two nanofiber membranes in the step (2) is 3:1-8:1, the rotation speed of the homogenizer is 12000-20000 r/min, and the homogenizing time is 10-30 min.
Further, the preparation method of the GO dispersion liquid in the step (2) is as follows: adding single-layer Graphene Oxide (GO) into deionized water, and performing ultrasonic dispersion for 2-10 hours to obtain a uniformly dispersed GO dispersion liquid with the mass concentration of 0.03% -0.1%; wherein the purity of the single-layer graphene oxide is 99 percent wt, the thickness is 0.6-1.0 nm, and the specific surface area is 1000-2/g。
Further, the imidization process of the polyamic acid nanofiber in the step (4) is as follows: heating to 350 deg.C from room temperature at a heating rate of 1.0-3.0 deg.C/min, respectively maintaining at 200 deg.C, 250 deg.C, 300 deg.C, and 350 deg.C for 30 min, 30 min, 30 min, and 60min, and naturally cooling to room temperature.
Further, in the step (4), the polyimide/nascent fiber composite aerogel after thermal imidization is subjected to temperature programming in a nitrogen atmosphere, and the specific parameters are as follows: heating from room temperature to 800 ℃ at the heating rate of 1-10 ℃/min, respectively keeping the temperature at 400 ℃, 500 ℃, 600 ℃,700 ℃ and 800 ℃ for 30-60min, and then naturally cooling to room temperature to obtain the porous composite aerogel.
Further, the gel electrolyte in the step (5) is prepared by the following method: mixing PVA with H2SO4:H2Mixing and stirring O according to the mass ratio of 1:1.5:10, swelling at 60 ℃ for 30-60min, and dissolving at 90 ℃ for 30-60min to obtain PVA/H2SO4A gel electrolyte.
The invention has the beneficial effects that:
(1) PI/ZrO prepared by the invention2The base carbon aerogel material has uniform pore size distribution, large specific surface area, high strength and small density, is an electrode material with excellent conductivity, and can be widely applied to the field of wearable energy supply.
(2) The invention utilizes simple electrostatic spinning method, freeze drying technology and carbonization process, the whole manufacturing process is simple and easy to operate, the cost is low, and the invention is environment-friendly.
(3) The super capacitor prepared by the method has the advantages of stable structure, stable chemical property, excellent electrochemical performance, good cycle performance, high specific capacitance and the like (0.2A g)-1The specific capacitance value is as high as 532.6F g-1) The method has great application potential in electrode materials of supercapacitors.
Drawings
FIG. 1 aerogel prior to carbonization;
FIG. 2 the carbonized aerogel;
FIG. 3 is an electron micrograph of the aerogel after carbonization;
figure 4 cyclic voltammograms of carbon aerogel-based capacitors.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Based on PI/ZrO2The preparation method of the nanofiber carbon aerogel flexible supercapacitor comprises the following steps:
(1) preparing 23% polyamic acid (PAA) spinning solution, dissolving for 6 h at 0 ℃ in an ice bath, wherein the solvent used in the polyamic acid spinning solution is N, N-dimethylacetamide, and the used simple substances are pyromellitic dianhydride (PMDA) and 4-4' -diaminodiphenyl ether (ODA), wherein: the mass ratio of ODA to PMDA =1: 1.02;
(2) preparing a zirconia nascent fiber spinning solution. Mixing n-basic zirconium Carbonate (CH)2O7Zr2): n acetic acid (CH)3COOH): n methanol (CH)3OH) =1:1:10, adding yttrium nitrate (Y) after uniformly mixing2O3）（CH2O7Zr2：Y2O3= 6%) is heated and stirred in a water bath kettle (the temperature is about 30-40 ℃, and the rotating speed is 500 r/min);
(3) preparing PAA nanofiber and zirconia as-spun fiber by an electrostatic spinning method;
(4) preparing a 0.05% single-layer Graphene Oxide (GO) aqueous solution, and performing ultrasonic dispersion for 9 hours to obtain a uniformly dispersed GO dispersion liquid;
(5) and (4) cutting the PAA nanofiber membrane and the nascent fiber membrane obtained in the step (3) into 1 × 1 cm nanofiber membrane small blocks, putting the small blocks into the GO dispersion obtained in the step (4) according to the mass fraction of 1.0%, and smashing the nanofiber membrane by using a high-speed homogenizer to form stable and uniform suspension. Wherein the mass ratio of the two nanofiber membranes is 3:1, the rotating speed of a homogenizer is 13000 r/min, and the homogenizing time is 20 min;
(6) pouring the nanofiber blending dispersion liquid obtained in the step (5) into a fixed container, freezing the nanofiber blending dispersion liquid into a solid by using liquid nitrogen or a refrigerator, putting the solid on a freeze dryer, and drying for 30 hours to obtain the composite nanofiber aerogel;
(7) putting the composite nanofiber aerogel obtained in the step (6) into a vacuum atmosphere box-type furnace, and setting a program to perform gradient temperature rise, wherein the temperature rise process comprises two processes: thermal imidization, high-temperature carbonization and formation of zirconia nanofibers of polyamic acid; the imidization process of the polyamic acid nanofiber comprises the following steps: heating to 350 deg.C from room temperature at a heating rate of 1.0-3.0 deg.C/min, respectively maintaining at 200 deg.C, 250 deg.C, 300 deg.C, and 350 deg.C for 30 min, 30 min, 30 min, and 60min, and naturally cooling to room temperature; performing temperature programming on the polyimide/nascent fiber composite aerogel subjected to thermal imidization in a nitrogen atmosphere, wherein the specific parameters are as follows: heating from room temperature to 800 ℃ at a heating rate of 1-10 ℃/min, respectively maintaining at 400 ℃, 500 ℃, 600 ℃,700 ℃ and 800 ℃ for 30 min (how long each temperature is controlled, a specific point value is written, the same is applied below), and naturally cooling to room temperature to obtain the porous composite aerogel;
(8) and (4) preparing a gel electrolyte. Mixing PVA with H2SO4：H2And mixing and stirring the O according to the mass ratio of 1:1.5: 10. Swelling at 60 deg.C for 45 min, and dissolving at 90 deg.C for 45 min to obtain PVA/H2SO4A gel electrolyte.
(9) And (3) coating the gel electrolyte on the surface of the porous composite aerogel (two aerogel electrode materials) carbonized at high temperature, and then standing in a constant-temperature and constant-pressure environment. And after 30 min, coating the gel electrolyte on an electrode material, and then putting the electrode material into a constant-temperature and constant-pressure environment. Repeating the steps several times, stacking two electrode materials together to form a sandwich structure, and assembling to obtain the polyimide/zirconium oxide (PI/ZrO/PI/ZrO) -based electrode2) A flexible supercapacitor of carbon aerogel.
Example 2
Based on PI/ZrO2The preparation method of the nanofiber carbon aerogel flexible supercapacitor comprises the following steps:
(1) preparing 23.5% polyamic acid (PAA) spinning solution, dissolving for 7 h at 0 ℃ in an ice bath, wherein the polyamic acid spinning solution uses N, N-dimethylacetamide as a solvent, and pyromellitic dianhydride (PMDA) and 4-4' -diaminodiphenyl ether (ODA) as simple substances, and the PAA spinning solution comprises the following components: the mass ratio of ODA to PMDA =1: 1.02;
(2) preparing a zirconia nascent fiber spinning solution. Mixing n-basic zirconium Carbonate (CH)2O7Zr2): n acetic acid (CH)3COOH): n methanol (CH)3OH) =1:1:10, adding yttrium nitrate (Y) after uniformly mixing2O3）（CH2O7Zr2：Y2O3= 6%) is heated and stirred in a water bath kettle (the temperature is about 30-40 ℃, and the rotating speed is 500 r/min);
(3) preparing PAA nanofiber and zirconia as-spun fiber by an electrostatic spinning method;
(4) preparing a 0.06% single-layer Graphene Oxide (GO) aqueous solution, and performing ultrasonic dispersion for 9 hours to obtain a uniformly dispersed GO dispersion liquid;
(5) and (4) cutting the PAA nanofiber membrane and the nascent fiber membrane obtained in the step (3) into 1 × 1 cm nanofiber membrane small blocks, putting the small blocks into the GO dispersion obtained in the step (4) according to the mass fraction of 1.0%, and smashing the nanofiber membrane by using a high-speed homogenizer to form stable and uniform suspension. Wherein the mass ratio of the two nanofiber membranes is 4:1, the rotating speed of a homogenizer is 13000 r/min, and the homogenizing time is 20 min;
(6) pouring the nanofiber blending dispersion liquid obtained in the step (5) into a fixed container, freezing the nanofiber blending dispersion liquid into a solid by using liquid nitrogen or a refrigerator, putting the solid on a freeze dryer, and drying for 30 hours to obtain the composite nanofiber aerogel;
(7) putting the composite nanofiber aerogel obtained in the step (6) into a vacuum atmosphere box-type furnace, and setting a program to perform gradient temperature rise, wherein the temperature rise process comprises two processes: thermal imidization, high-temperature carbonization and formation of zirconia nanofibers of polyamic acid; the imidization process of the polyamic acid nanofiber comprises the following steps: heating to 350 deg.C from room temperature at a heating rate of 1.0-3.0 deg.C/min, respectively maintaining at 200 deg.C, 250 deg.C, 300 deg.C, and 350 deg.C for 30 min, 30 min, 30 min, and 60min, and naturally cooling to room temperature; performing temperature programming on the polyimide/nascent fiber composite aerogel subjected to thermal imidization in a nitrogen atmosphere, wherein the specific parameters are as follows: heating from room temperature to 800 ℃ at the heating rate of 1-10 ℃/min, respectively keeping the temperature at 400 ℃, 500 ℃, 600 ℃,700 ℃ and 800 ℃ for 30 min, and then naturally cooling to room temperature to obtain the porous composite aerogel;
(8) and (4) preparing a gel electrolyte. Mixing PVA with H2SO4：H2And mixing and stirring the O according to the mass ratio of 1:1.5: 10. Swelling at 60 deg.C for 45 min, and dissolving at 90 deg.C for 45 min to obtain PVA/H2SO4A gel electrolyte;
(9) and (3) coating the gel electrolyte on the surface of the porous composite aerogel (two aerogel electrode materials) carbonized at high temperature, and then standing in a constant-temperature and constant-pressure environment. And after 30 min, coating the gel electrolyte on an electrode material, and then putting the electrode material into a constant-temperature and constant-pressure environment. Repeating the steps several times, stacking two electrode materials together to form a sandwich structure, and assembling to obtain the polyimide/zirconium oxide (PI/ZrO/PI/ZrO) -based electrode2) A flexible supercapacitor of carbon aerogel.
The electrostatic spinning nanofiber-based composite carbon aerogel electrode material prepared by the invention has the advantages of uniform pore size distribution, large specific surface area, high strength, small density, excellent mechanical property, compression resilience, good conductivity, stable chemical property, excellent electrochemical property, good cycle performance, high specific capacitance, simple preparation method, strong controllability, no additional auxiliary agent and the like, and has good application prospect in the field of flexible supercapacitor electrode materials.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. Based on PI/ZrO2The preparation method of the nanofiber carbon aerogel flexible supercapacitor is characterized by comprising the following steps: spinning a nanofiber membrane by an electrostatic spinning technology, crushing the nanofiber membrane into a dispersion liquid of graphene oxide to form a uniform and stable nanofiber suspension, freezing the suspension into a solid by using liquid nitrogen or a refrigerator, preparing a nanofiber aerogel by using a freeze-drying technology, carbonizing the aerogel at a high temperature to form a carbon nanofiber aerogel, and finally assembling the carbon nanofiber aerogel with a gel electrolyte to obtain the supercapacitor; the method specifically comprises the following steps:
(1) preparing a polyamic acid (PAA) spinning solution and a zirconia nascent fiber spinning solution, and preparing a polyamic acid (PAA) nanofiber membrane and a zirconia nascent fiber membrane by an electrostatic spinning method, wherein the diameter of the nanofiber is 100-600 nm;
(2) cutting the polyamide acid (PAA) nanofiber membrane and the zirconia nascent fiber membrane obtained in the step (1) into small pieces, putting the small pieces into Graphene Oxide (GO) dispersion liquid according to the mass fraction of 0.6-1.5%, and smashing the nanofiber membrane by using a high-speed homogenizer to form stable and uniform nanofiber blending dispersion liquid;
(3) pouring the nanofiber blending dispersion liquid obtained in the step (2) into a mold, freezing the nanofiber blending dispersion liquid into a solid by using liquid nitrogen or a refrigerator, and placing the solid on a freeze dryer for drying for 20-45 hours to obtain the composite nanofiber aerogel;
(4) putting the composite nanofiber aerogel obtained in the step (3) into a vacuum atmosphere box-type furnace, and setting a program to perform gradient temperature rise, wherein the temperature rise process comprises two processes: thermal imidization, high-temperature carbonization and formation of zirconia nanofibers of polyamic acid; obtaining the porous composite aerogel;
(5) coating the gel electrolyte on one surface of the porous composite aerogel carbonized at high temperature, standing for 30 min, coating the gel electrolyte on the electrode materials, repeating for 2-5 times, overlapping the surfaces of the two electrode materials coated with the gel electrolyte to form a sandwich structure, and assembling to obtain the composite aerogel based on the structurePolyimide/zirconia (PI/ZrO)2) A flexible supercapacitor of carbon aerogel.
2. The method of claim 1, wherein: the preparation method of the polyamic acid (PAA) spinning solution in the step (1) comprises the following steps: adding pyromellitic dianhydride (PMDA) and 4-4' -diaminodiphenyl ether (ODA) into N, N-dimethylacetamide according to the mass ratio of ODA: PMDA =1:1.02, and dissolving for 3-10 h at 0 ℃ in an ice bath to obtain a polyamic acid (PAA) spinning solution with the mass concentration of 21% -25%.
3. The method of claim 1, wherein: the preparation method of the zirconia nascent fiber spinning solution in the step (1) comprises the following steps: uniformly mixing basic zirconium carbonate, acetic acid and methanol, then adding yttrium nitrate, heating and stirring at the temperature of 30-40 ℃, and uniformly mixing to obtain a zirconium oxide nascent fiber spinning solution; wherein n basic zirconium Carbonate (CH)2O7Zr2): n acetic acid (CH)3COOH): n methanol (CH)3OH) =1:1:10, yttrium nitrate (Y)2O3) In the mass ratio of zirconium basic Carbonate (CH)2O7Zr2) 6% of the mass.
4. The method of claim 1, wherein: the electrostatic spinning process parameters in the step (1) are as follows: the voltage is 15-30 kV, the used spinning container is a 10 mL plastic injector with a pinhole diameter of 0.5 mm, the flow rate is 0.06-0.5 mm/min, the receiving distance is 10-20 cm, the spinning temperature is 20-35 ℃, and the humidity is 25-50 RH%.
5. The method of claim 1, wherein: the mass ratio of the two nanofiber membranes in the step (2) is 3:1-8:1, the rotation speed of a homogenizer is 12000-20000 r/min, and the homogenizing time is 10-30 min.
6. The method of claim 1, wherein: said step (2)The preparation method of the medium GO dispersion liquid comprises the following steps: adding single-layer Graphene Oxide (GO) into deionized water, and performing ultrasonic dispersion for 2-10 hours to obtain a uniformly dispersed GO dispersion liquid with the mass concentration of 0.03% -0.1%; wherein the purity of the single-layer graphene oxide is 99 percent wt, the thickness is 0.6-1.0 nm, and the specific surface area is 1000-2/g。
7. The method of claim 1, wherein: the imidization process of the polyamic acid nano-fiber in the step (4) is as follows: heating to 350 deg.C from room temperature at a heating rate of 1.0-3.0 deg.C/min, respectively maintaining at 200 deg.C, 250 deg.C, 300 deg.C, and 350 deg.C for 30 min, 30 min, 30 min, and 60min, and naturally cooling to room temperature.
8. The method of claim 1, wherein: in the step (4), the polyimide/zirconia nascent fiber composite aerogel after thermal imidization is subjected to temperature programming in a nitrogen atmosphere, and the specific parameters are as follows: heating from room temperature to 800 ℃ at the heating rate of 1-10 ℃/min, respectively keeping the temperature at 400 ℃, 500 ℃, 600 ℃,700 ℃ and 800 ℃ for 30-60min, and then naturally cooling to room temperature to obtain the porous composite aerogel.
9. The method of claim 1, wherein: the preparation method of the gel electrolyte in the step (5) is as follows: mixing PVA with H2SO4:H2Mixing and stirring O according to the mass ratio of 1:1.5:10, swelling at 60 ℃ for 30-60min, and dissolving at 90 ℃ for 30-60min to obtain PVA/H2SO4A gel electrolyte.
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| KR101676688B1 (en) * | 2014-01-13 | 2016-11-29 | 울산과학기술원 | Micro porous hybrid separator, method for manufacturing the same and electrochemical device containing the same |
| CN104355302B (en) * | 2014-10-21 | 2016-04-20 | 复旦大学 | The preparation method of a kind of Graphene/polyimide-based carbon aerogels |
| CN105845455B (en) * | 2016-05-10 | 2019-05-03 | 复旦大学 | Polyacrylonitrile/polyimide-based composite carbon gas gel electrode material and preparation method |
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