CN111048322A - Carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode and preparation method and application thereof - Google Patents
Carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000008273 gelatin Substances 0.000 title claims abstract description 88
- 229920000159 gelatin Polymers 0.000 title claims abstract description 88
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 108010010803 Gelatin Proteins 0.000 claims abstract description 52
- 235000019322 gelatine Nutrition 0.000 claims abstract description 52
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 52
- 229920000767 polyaniline Polymers 0.000 claims abstract description 43
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 42
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 42
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 23
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940068041 phytic acid Drugs 0.000 claims abstract description 23
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 23
- 239000000467 phytic acid Substances 0.000 claims abstract description 23
- 238000002791 soaking Methods 0.000 claims abstract description 19
- 238000004146 energy storage Methods 0.000 claims abstract description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 58
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical class [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 2
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000003990 capacitor Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000005452 bending Methods 0.000 description 8
- 239000000017 hydrogel Substances 0.000 description 8
- 238000000502 dialysis Methods 0.000 description 6
- 238000002848 electrochemical method Methods 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
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- 238000001035 drying Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000004151 quinonyl group Chemical group 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
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- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- Nanotechnology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract
The invention discloses a carbon nano tube-polyaniline-gelatin semi-interpenetrating network flexible electrode and a preparation method and application thereof, wherein polyaniline with good pseudocapacitance and treated by phytic acid grows in situ in a highly conductive carbon nano tube to be coated and is introduced into gelatin with a coil structure, and the high-strength flexible electrode of the carbon nano tube-polyaniline/gelatin semi-interpenetrating network is prepared by directly soaking the polyaniline with ammonium sulfate solution by utilizing Hofmeister effect, so that the flexible electrode has good mechanical property and electrochemical energy storage property, and has good application prospect in the fields of flexible and wearable energy storage devices.
Description
Technical Field
The invention belongs to the technical field of electrodes, and particularly relates to a carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode and a preparation method and application thereof.
Background
With the development of flexible electronics, wearable electronic devices are rapidly entering the lives of people. In order to realize the commercialization of wearable devices, the energy supply components of the wearable devices also need to be flexible and have high performance, and therefore, the high-performance flexible energy storage devices will increasingly show potential market values. Have received a great deal of attention. However, after the supercapacitor is subjected to bending deformation, the polyelectrolyte layer remains good, the electrode material structure is often damaged, and the energy storage characteristics are degraded. The application of the super capacitor in the field of flexible wearable is severely limited due to the lack of mechanical properties of the electrode material, so that the development of the flexible super capacitor with mechanical properties and energy storage properties still faces huge challenges.
Although the carbon-based material has excellent electrical conductivity, high specific surface area and good mechanical properties, the flexible carbon electrode has low tensile strength, low elongation at break and low specific capacity. The flexible electrode material based on the flexible polymer hydrogel has the defects of complex synthesis process and the like, and most of raw materials of the used crosslinking agent are expensive and toxic, so the practical application of the flexible electrode material is limited. Gelatin is an environment-friendly material and has no pollution; from the economic point of view, the proposal omits a plurality of intermediate processes, prepares the flexible hydrogel in one step, saves a plurality of costs, and has rich sources and low price. However, the hydrogel obtained by the gelatin which is a macromolecular hydrophilic colloid has low breaking elongation and low tensile strength, and the mechanical strength of the gelatin hydrogel can be effectively improved by directly soaking the gelatin hydrogel in ammonium sulfate through the Hofmeis special effect. By introducing polyaniline and carbon nanotubes into the high-strength gelatin hydrogel, the strength and toughness of the electrode are enhanced, and the electrode has good electrochemical performance. Meanwhile, phytic acid is selected as a cross-linking agent to protonate the quinone nitrogen on aniline, thereby forming a gel network. The method does not need to modify the raw materials and add any chemical cross-linking agent, can greatly enhance the mechanical property of the flexible electrode material through simple operation, has good application prospect in the fields of flexible and wearable energy storage devices, and is expected to be used for large-scale industrial production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode and a preparation method and application thereof.
The technical purpose of the invention is realized by the following technical scheme.
A carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode and a preparation method thereof are carried out according to the following steps:
Uniformly dispersing carbon nanotubes in water to form suspension of the carbon nanotubes, adding aniline and phytic acid into the suspension and uniformly dispersing to form reaction liquid, adding an initiator into the reaction liquid, and reacting under the condition of stirring ice bath to obtain carbon nanotube-polyaniline, wherein the mass ratio of aniline to carbon nanotubes is (5-20): 1, the volume ratio of the phytic acid to the aniline is (1-3): 1;
in the step 1, ultrasonic stirring or mechanical stirring is adopted for uniform dispersion, and the stirring speed is 200-500 revolutions.
In step 1, the carbon nano-tube is uniformly dispersed in water, the dispersion time is 30-120 min, and the concentration is 0.01-0.03 g/ml.
In the step 1, the mass ratio of aniline to carbon nanotubes is (10-16): 1, the volume ratio of the phytic acid to the aniline is (1.5-2): 1.
in the step 1, the initiator is ammonium persulfate or potassium persulfate, and the molar ratio of the initiator to the aniline is (0.05-0.1): 1, if an initiator aqueous solution is used, adding the initiator, wherein the concentration of the initiator is 0.5-2 mmol/L.
In step 1, the reaction is carried out for 10-120s under the condition of stirring ice bath, and is kept still for 8-16 hours under the condition of ice bath.
In step 1, after the reaction is finished, the supernatant is poured off to obtain a precipitate, namely the carbon nano tube-polyaniline.
Step 2, preparation of carbon nano tube-polyaniline-gelatin
Uniformly dispersing the carbon nano tube-polyaniline prepared in the step 1 in water, adding gelatin, stirring and reacting for 0.5-2 hours under the condition of water bath at the temperature of 30-60 ℃, dialyzing a product (mixed liquid), and pouring into a mold for molding to obtain the carbon nano tube-polyaniline-gelatin;
in step 2, the reaction temperature is 40-50 ℃ and the reaction time is 1-2 hours.
In step 2, dialysis bags of number average molecular weight 3000 were selected for dialysis for 1 to 7 days, 24 hours per day.
In the step 2, when the material is formed in a mould, the room temperature is 20-25 ℃, the normal pressure is selected, and the time is 5-20 hours.
In step 2, the mass percentage of gelatin is 5-15%, i.e., gelatin mass/(gelatin + water + carbon nanotube-polyaniline prepared in step 1) × 100%, preferably 10-15%.
Step 3, toughening and reinforcing the carbon nano tube-polyaniline-gelatin
And (3) soaking the carbon nano tube-polyaniline-gelatin obtained in the step (2) in a saturated ammonium persulfate aqueous solution to strengthen and toughen the gelatin, and then carrying out vacuum drying to obtain the toughened and strengthened carbon nano tube-polyaniline-gelatin, namely the carbon nano tube-polyaniline-gelatin semi-interpenetrating network flexible electrode.
In step 3, the soaking time is 5 to 20 hours, preferably 10 to 16 hours.
In step 3, placing a saturated ammonium persulfate aqueous solution in an ice bath condition, and when the temperature is stabilized at 0-5 ℃, placing the carbon nano tube-polyaniline-gelatin in the saturated ammonium persulfate aqueous solution for soaking and keeping the temperature at 0-5 ℃ within the soaking time.
Compared with the prior art and materials, the carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode prepared by the invention has the advantages of simple experimental method, easily-achieved experimental conditions, environmental friendliness, effective improvement on the mechanical strength of the carbon-based material, and good mechanical property and electrochemical energy storage property, so that the carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode has good application prospect in the fields of flexible and wearable energy storage devices.
Drawings
FIG. 1 is a schematic diagram of the principle route of the present invention for preparing carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode.
FIG. 2 is an infrared spectrum of the carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode prepared by the present invention.
Fig. 3 is an electrochemical performance test chart (i.e., cyclic voltammetry curve) of the carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode prepared by the present invention.
Fig. 4 is an electrochemical performance test chart (i.e., constant current charge-discharge diagram) of the carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode prepared by the invention.
FIG. 5 is a scanning electron micrograph of the cross section of the carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode prepared by the present invention.
FIG. 6 is a photograph of the shape of the carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode prepared by the present invention before and after 180 degree bending.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples. The raw materials used in the examples of the invention are all commercial products, and the purity is analytical purity. The microscopic morphology of the flexible electrode prepared by the invention is displayed by a Scanning Electron Microscope (SEM), and a Japanese Hitachi S4800 type scanning electron microscope is adopted; the chemical structure of the flexible electrode is displayed by infrared spectrum, and an infrared spectrometer of Nicolet 6700 model of Nicolet is adopted; and carrying out electrochemical test on the sample by adopting a three-electrode test system. The dialysis bag with the number average molecular weight of 3000 is selected for dialysis, 24 hours per day, and when the dialysis bag is formed in a mold, the dialysis bag is selected to be at the room temperature of 20-25 ℃ and normal pressure for 10 hours.
Example 1
Taking 0.03g of carbon nano tube, carrying out ultrasonic dispersion in 30ml of water for 30 minutes, adding aniline into the turbid solution according to the mass ratio of polyaniline to the carbon nano tube of 10:1, and adding phytic acid according to the volume ratio of phytic acid to aniline of 2: 1. Adding ammonium persulfate solution with the concentration of 1mmol/L into the reaction solution, rapidly stirring for 30 seconds, and standing for 12 hours at the temperature of 4 ℃. Adding 10 percent gelatin by mass, and stirring for 0.5 hour under the condition of water bath at 40 ℃. Dialyzing the mixed solution for 1 day, pouring the mixed solution into a mold for molding, soaking the mixed solution in a saturated ammonium persulfate solution for 15 hours at the temperature of 4 ℃, and performing vacuum drying at the temperature of 60 ℃. The flexible electrode material can be bent by 180 degrees and used as a flexible electrode material of a super capacitor for electrochemical characterization, wherein the flexible electrode material is 0.5Ag-1The capacity of the capacitor can be stabilized at 215F g-1(ii) a At 0.25A g-1At a current density of 322Fg, a specific capacity of 322Fg can be obtained-1。
Example 2
Taking 0.03g of carbon nano tube, carrying out ultrasonic dispersion in 30ml of water for 30 minutes, adding aniline into the turbid solution according to the mass ratio of polyaniline to the carbon nano tube of 8:1, and adding phytic acid according to the volume ratio of phytic acid to aniline of 2: 1. Adding ammonium persulfate solution with the concentration of 1mmol/L into the reaction solution, rapidly stirring for 30 seconds, and standing for 16 hours at the temperature of 4 ℃. Adding 12% gelatin, and stirring for 0.5 hr at 40 deg.C in water bath. Dialyzing the mixed solution for 1 day, pouring the mixed solution into a mold, soaking the mixed solution in a saturated ammonium persulfate solution for 18 hours at the temperature of 5 ℃, and drying the mixed solution in vacuum at the temperature of 60 ℃. The flexible electrode material can be bent by 180 degrees and used as a flexible electrode material of a super capacitor for electrochemical characterization, wherein the flexible electrode material is 0.5Ag-1The capacity of the capacitor can be stabilized at 191F g-1(ii) a At 0.25A g-1At a current density of (2), a specific capacity of 295Fg can be obtained-1。
Example 3
Taking 0.03g of carbon nano tube, carrying out ultrasonic dispersion in 30ml of water for 30 minutes, adding aniline into turbid liquid according to the mass ratio of polyaniline to the carbon nano tube of 15:1, and adding phytic acid and phytic acidAdding phytic acid into aniline with the volume ratio of 3: 1. Adding ammonium persulfate solution with the concentration of 1.5mmol/L into the reaction solution, rapidly stirring for 30 seconds, and standing for 10 hours at the temperature of 4 ℃. Adding gelatin with the mass fraction of 8%, and stirring for 0.5 hour under the condition of water bath at 40 ℃. Dialyzing the mixed solution for 1 day, pouring the mixed solution into a mold, soaking the mixed solution in a saturated ammonium persulfate solution for 12 hours at the temperature of 4 ℃, and drying the mixed solution in vacuum at the temperature of 60 ℃. The flexible electrode material can be bent by 180 degrees and used as a flexible electrode material of a super capacitor for electrochemical characterization, wherein the flexible electrode material is 0.5Ag-1The capacity of the capacitor can be stabilized at 195F g-1(ii) a At 0.25A g-1At a current density of (3), a specific capacity of 301Fg-1。
Example 4
Taking 0.03g of carbon nano tube, carrying out ultrasonic dispersion in 30ml of water for 30 minutes, adding aniline into the turbid solution according to the mass ratio of polyaniline to the carbon nano tube of 12:1, and adding phytic acid according to the volume ratio of phytic acid to aniline of 3: 1. Adding ammonium persulfate solution with the concentration of 1.5mmol/L into the reaction solution, rapidly stirring for 30 seconds, and standing for 10 hours at the temperature of 4 ℃. Adding gelatin with the mass fraction of 8%, and stirring for 0.5 hour under the condition of water bath at 40 ℃. Dialyzing the mixed solution for 1 day, pouring the mixed solution into a mold, soaking the mixed solution in a saturated ammonium persulfate solution for 24 hours at the temperature of 6 ℃, and drying the mixed solution in vacuum at the temperature of 60 ℃. The flexible electrode material can be bent by 180 degrees and used as a flexible electrode material of a super capacitor for electrochemical characterization, and the electrochemical characterization is carried out at 0.5 A.g-1The capacity of the capacitor can be stabilized at 207F g at the current density of (1)-1(ii) a At 0.25 A.g-1The specific capacity of the obtained product is 293F g-1。
Example 5
Taking 0.03g of carbon nano tube, carrying out ultrasonic dispersion in 30ml of water for 30 minutes, adding aniline into the turbid liquid according to the mass ratio of polyaniline to the carbon nano tube of 15:1, and adding phytic acid according to the volume ratio of phytic acid to aniline of 3: 1. Adding ammonium persulfate solution with the concentration of 1.2mmol/L into the reaction solution, rapidly stirring for 30 seconds, and standing for 15 hours at the temperature of 4 ℃. Adding 12% gelatin, and stirring for 0.5 hr at 40 deg.C in water bath. Dialyzing the mixed solution for 1 day, pouring the mixed solution into a mould, soaking the mixed solution in a saturated ammonium persulfate solution for 18 hours at the temperature of 6 DEG CAnd vacuum drying at 60 deg.C. The flexible electrode material can be bent by 180 degrees and used as the flexible electrode material of the super capacitor for electrochemical characterization, and the bending angle is 0.5Ag-1The capacity of the capacitor can be stabilized at 201F g-1(ii) a At 0.25A g-1At a current density of 313Fg, a specific capacity of 313Fg can be obtained-1。
As can be seen from the above examples, the mass fraction of gelatin is critical and can affect the flexibility and electrochemical performance of the flexible electrode to different degrees. If the mass fraction of the gelatin is too high, the electrochemical performance of the flexible electrode is reduced. If the mass fraction of gelatin is too low, the mechanical properties of the flexible electrode will be reduced. When the mass fraction of the gelatin is proper, the obtained flexible electrode has good mechanical properties and electrochemical energy storage properties.
The carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode prepared by the method is characterized. As can be seen from FIG. 2, in the high strength gelatin hydrogel, 3415cm-1The corresponding part is a stretching vibration absorption peak of-OH bond, and the characteristic peak is wider. 1641cm-1Is located at 1398cm and is a vibration absorption peak of amido bond-1Bending vibration at C-H bond and-CH3Symmetric vibration absorption peaks of the bonds. As can be seen from the characteristic peak of 10% carbon nanotube/gelatin, the stretching vibration intensity of the-OH bond after the carbon nanotube is doped into the gelatin hydrogel is 3415cm-1Reduced to 3132cm-1. And the bond is located at 1647cm-1The peak of vibration absorption of amide bond at 1410cm-1C-H bond bending vibration and-CH3The symmetrical vibration absorption peak of the bond can prove that the carbon nano tube is well combined with the gelatin. The carbon nano tube adopted in the method has high purity after purification, and the carbon nano tube is easy to absorb infrared, so that the infrared spectrum of the carbon nano tube can hardly detect a characteristic peak. Analyzing each absorption peak of the carbon nano tube-polyaniline/gelatin flexible electrode, which is 3130cm-1A stretching vibration peak at-OH bond of 1575cm-1Characteristic peak and 1486cm-1The characteristic peaks at (a) are due to stretching vibrations of the quinone ring and the benzene ring, respectively. 1407cm-1Bending vibration at C-H bond and-CH3Symmetric vibration of keyDynamic absorption peak. At 1300cm-1The band (B) is a C-N stretching vibration absorption peak of a secondary aromatic amine having aromatic conjugation. 1140cm-1The bending vibration absorption peak at N ═ Q ═ N (Q represents a quinone ring), which also indicates electron separation in PANI. 798cm-1And 506cm-1And the position is a bending vibration absorption peak of a C-H bond in the 1, 4-disubstituted aromatic ring. The characteristic peaks of the gelatin are retained and no new peak is generated by combining the infrared spectrogram, which proves that the phytic acid crosslinked polyaniline-coated carbon nano tube is successfully synthesized and the gelatin is successfully introduced.
As shown in attached fig. 3 and 4, the cyclic voltammetry curve has good symmetry, and the specific capacity of the cyclic voltammetry curve with a scanning rate of 5mV/s under a voltage window of-0.2-0.8V can be calculated by a calculation method of the cyclic voltammetry curve to be 338.7F/g, which is higher than that of a carbon nanotube/gelatin electrode and a polyaniline/gelatin electrode, so that the semi-interpenetrating network well retains the good specific capacity of the polyaniline as a pseudocapacitance material; under the current density of 0.25A/g, the discharge time reaches 1291s, the specific capacity is 322F/g, and the specific capacity is better than that of carbon nano tube/gelatin and polyaniline/gelatin.
As shown in fig. 5, the appearance of the prepared product sample is observed by using a scanning electron microscope, and it can be seen that the interior of the electrode shows a porous structure, which is beneficial to the permeation of electrolyte, so as to provide an ion transmission channel, and the carbon nanotubes have no agglomeration phenomenon, polyaniline and gelatin are uniformly coated on the carbon nanotubes, and the polyaniline-coated carbon nanotubes are mutually overlapped to form an electron transmission channel. The phytic acid crosslinked polyaniline coats the carbon nano tube and grows in situ on the carbon nano tube, so that the excellent characteristic of introducing the polyaniline as a pseudo-capacitor material is realized on the premise of keeping the performance of the carbon nano tube. As shown in fig. 6, the carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode prepared by the invention can be bent by 180 degrees, still maintains good appearance, has considerable flexibility, effectively improves the mechanical strength of the carbon-based material, and has good mechanical properties and electrochemical energy storage properties.
The preparation of the carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode can be realized by adjusting the process parameters according to the content of the invention, and the performance basically consistent with the invention is shown, namely the application of the carbon nanotube-polyaniline/gelatin semi-interpenetrating network flexible electrode in flexible and wearable energy storage devices. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode is characterized by comprising the following steps:
step 1, preparation of carbon nanotube-polyaniline
Uniformly dispersing carbon nanotubes in water to form suspension of the carbon nanotubes, adding aniline and phytic acid into the suspension and uniformly dispersing to form reaction liquid, adding an initiator into the reaction liquid, and reacting under the condition of stirring ice bath to obtain carbon nanotube-polyaniline, wherein the mass ratio of aniline to carbon nanotubes is (5-20): 1, the volume ratio of the phytic acid to the aniline is (1-3): 1;
step 2, preparation of carbon nano tube-polyaniline-gelatin
Uniformly dispersing the carbon nano tube-polyaniline prepared in the step 1 in water, adding gelatin, stirring and reacting for 0.5-2 hours under the condition of water bath at the temperature of 30-60 ℃, dialyzing a product (mixed liquid), and pouring into a mold for molding to obtain the carbon nano tube-polyaniline-gelatin;
step 3, toughening and reinforcing the carbon nano tube-polyaniline-gelatin
And (3) soaking the carbon nano tube-polyaniline-gelatin obtained in the step (2) in a saturated ammonium persulfate aqueous solution to strengthen and toughen the gelatin, and then carrying out vacuum drying to obtain the toughened and strengthened carbon nano tube-polyaniline-gelatin, namely the carbon nano tube-polyaniline-gelatin semi-interpenetrating network flexible electrode.
2. The carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode of claim 1, wherein in step 1, the carbon nanotube is uniformly dispersed in water for 30-120 min at a concentration of 0.01-0.03 g/ml; the mass ratio of the aniline to the carbon nano tube is (10-16): 1, the volume ratio of the phytic acid to the aniline is (1.5-2): 1; the reaction is carried out for 10-120s under the condition of stirring ice bath, and is kept still for 8-16 hours under the condition of ice bath.
3. The carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode according to claim 1, wherein in step 1, the initiator is ammonium persulfate or potassium persulfate, and the molar ratio of the initiator to the aniline is (0.05-0.1): 1, if an initiator aqueous solution mode is used, adding the initiator, wherein the concentration of the initiator is 0.5-2 mmol/L; the ultrasonic stirring or the mechanical stirring is adopted for uniform dispersion, and the stirring speed is 200-500 turns.
4. The carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode according to claim 1, wherein in step 2, the reaction temperature is 40-50 ℃ and the reaction time is 1-2 hours; when the material is molded in a mold, the room temperature is 20-25 ℃, the normal pressure is selected, and the time is 5-20 hours; the mass percent of the gelatin is 5-15%, preferably 10-15%.
5. The carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode according to claim 1, wherein in step 3, the soaking time is 5 to 20 hours, preferably 10 to 16 hours; placing a saturated ammonium persulfate aqueous solution in an ice bath condition, placing the carbon nano tube-polyaniline-gelatin in the saturated ammonium persulfate aqueous solution for soaking when the temperature is stabilized at 0-5 ℃, and keeping the temperature at 0-5 ℃ in the soaking time.
6. A preparation method of a carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode is characterized by comprising the following steps:
step 1, preparation of carbon nanotube-polyaniline
Uniformly dispersing carbon nanotubes in water to form suspension of the carbon nanotubes, adding aniline and phytic acid into the suspension and uniformly dispersing to form reaction liquid, adding an initiator into the reaction liquid, and reacting under the condition of stirring ice bath to obtain carbon nanotube-polyaniline, wherein the mass ratio of aniline to carbon nanotubes is (5-20): 1, the volume ratio of the phytic acid to the aniline is (1-3): 1;
step 2, preparation of carbon nano tube-polyaniline-gelatin
Uniformly dispersing the carbon nano tube-polyaniline prepared in the step 1 in water, adding gelatin, stirring and reacting for 0.5-2 hours under the condition of water bath at the temperature of 30-60 ℃, dialyzing a product (mixed liquid), and pouring into a mold for molding to obtain the carbon nano tube-polyaniline-gelatin;
step 3, toughening and reinforcing the carbon nano tube-polyaniline-gelatin
And (3) soaking the carbon nano tube-polyaniline-gelatin obtained in the step (2) in a saturated ammonium persulfate aqueous solution to strengthen and toughen the gelatin, and then carrying out vacuum drying to obtain the toughened and strengthened carbon nano tube-polyaniline-gelatin, namely the carbon nano tube-polyaniline-gelatin semi-interpenetrating network flexible electrode.
7. The method for preparing the carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode as claimed in claim 6, wherein in the step 1, the carbon nanotube is uniformly dispersed in water for 30-120 min at a concentration of 0.01-0.03 g/ml; the mass ratio of the aniline to the carbon nano tube is (10-16): 1, the volume ratio of the phytic acid to the aniline is (1.5-2): 1; reacting for 10-120s under the condition of stirring ice bath, and standing for 8-16 h under the condition of ice bath; the initiator is ammonium persulfate or potassium persulfate, and the molar ratio of the initiator to the aniline is (0.05-0.1): 1, if an initiator aqueous solution mode is used, adding the initiator, wherein the concentration of the initiator is 0.5-2 mmol/L; the ultrasonic agitation or mechanical agitation is adopted for uniform dispersion, and the agitation speed is 200-500 turns.
8. The method for preparing the carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode as claimed in claim 6, wherein in the step 2, the reaction temperature is 40-50 ℃ and the reaction time is 1-2 hours; when the material is formed in a mould, the room temperature is 20-25 ℃, the normal pressure is selected, and the time is 5-20 hours; the mass percent of gelatin is 5-15%, preferably 10-15%.
9. The method for preparing the carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode according to claim 6, wherein in the step 3, the soaking time is 5 to 20 hours, preferably 10 to 16 hours; placing a saturated ammonium persulfate aqueous solution in an ice bath condition, placing the carbon nano tube-polyaniline-gelatin in the saturated ammonium persulfate aqueous solution for soaking when the temperature is stabilized at 0-5 ℃, and keeping the temperature at 0-5 ℃ in the soaking time.
10. Use of the carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode of any one of claims 1-5 in a flexible or wearable energy storage device.
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