CN114709088A - Preparation of polyaniline/conductive carbon black composite material and construction of self-repairing high-voltage super-electric device - Google Patents

Preparation of polyaniline/conductive carbon black composite material and construction of self-repairing high-voltage super-electric device Download PDF

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CN114709088A
CN114709088A CN202210385981.0A CN202210385981A CN114709088A CN 114709088 A CN114709088 A CN 114709088A CN 202210385981 A CN202210385981 A CN 202210385981A CN 114709088 A CN114709088 A CN 114709088A
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self
solution
carbon black
polyaniline
conductive carbon
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闫健
余少伟
汪震
吴玉程
刘家琴
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Hefei University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses preparation of a polyaniline/conductive carbon black composite material and construction of a self-repairing high-voltage super-electric device. The invention synthesizes the composite material with special morphology, which has better capacity and conductivity and effectively improves the electrochemical performance. The invention utilizes the synthesized composite material and the self-repairing polymer to manufacture the symmetrical and asymmetrical super-electric devices with the self-repairing function. And the double-gel electrolyte is used for improving the window of the device, and a solution is provided for solving the problems of poor circulation and low energy density of the polyaniline super-electric appliance.

Description

Preparation of polyaniline/conductive carbon black composite material and construction of self-repairing high-voltage super-electric device
Technical Field
The invention belongs to the field of electrochemical energy storage, and particularly relates to preparation of a polyaniline/conductive carbon black composite material and construction of a self-repairing high-voltage super-electric device.
Background
With the rapid increase of energy consumption and the increasing severity of environmental pollution problems, the development of clean and sustainable new energy becomes an important task in the development of the current society. Among various energy storage devices, supercapacitors (also called electrochemical capacitors) have higher specific energy than conventional capacitors, higher specific power and excellent cycle life than secondary batteries, are rapidly charged, environmentally friendly and have low maintenance cost, and have been widely regarded in recent years, wherein high-performance electrode materials are key parts of the supercapacitors.
The appearance of the conductive polymer provides a new idea for the research of the electrode material of the supercapacitor. Among many conductive polymers, polyaniline has been widely spotlighted because of its simple preparation, low cost, good redox reversibility and high specific capacity. However, polyaniline is not perfect as a super-electric material, and has the following disadvantages: (1) in the process of charging and discharging, the structure of polyaniline molecules which are microscopically favorable for energy storage is greatly damaged due to contraction/expansion of polyaniline molecular chains caused by ion transmission, and then the transmission capability of ions in the polyaniline molecules is increasingly poor, so that the circulation stability is poor. (2) The polyaniline devices have a narrow operating window resulting in a relatively low energy density.
Conductive carbon black, a common carbon material, has the characteristics of high specific surface area, high structure, high purity and excellent conductivity, and is mainly used as a conductive agent for capacitors and batteries.
The self-repairing material is an organic compound synthesized at high temperature, and polyaniline of which the structure is damaged due to contraction/expansion caused by ion transmission can be reconnected and repaired in a hydrogen bonding mode, so that the cycle performance of the polyaniline super capacitor is improved.
There are several development directions for the development of polyaniline supercapacitors:
(1) the controllable preparation of the polyaniline micro-morphology is realized by adjusting and designing polymerization conditions;
(2) the polymer chain structure of polyaniline is designed and optimized, and the volume change is inhibited by using methods such as copolymerization, crosslinking and substitution, so that the service life is prolonged;
(3) the polyaniline electrode material generally has the defect of low energy density, and is necessary to research polyaniline and composite materials thereof with high energy density.
The invention provides a solution to two main problems faced by polyaniline super-electric devices, firstly, self-repairing polymers are added to improve the cycle performance of the polyaniline device when electrode materials are manufactured; and secondly, the working window of the polyaniline super-electric device is improved by using a double-gel method, so that the energy density of the polyaniline super-electric device is improved.
Disclosure of Invention
The invention aims to provide preparation of a polyaniline/conductive carbon black composite material and construction of a self-repairing high-voltage super-electric device. The invention synthesizes the composite material with special morphology, which has better capacity and conductivity and effectively improves the electrochemical performance. The invention utilizes the synthesized composite material and the self-repairing polymer to manufacture the symmetrical and asymmetrical super-electric devices with the self-repairing function. And the double-gel electrolyte is used for improving the window of the device, and a solution is provided for solving the problems of poor circulation and low energy density of the polyaniline super-electric appliance.
The preparation method of the polyaniline/conductive carbon black composite material comprises the following steps:
step 1: ultrasonically dispersing the passivated conductive carbon black in deionized water, uniformly dispersing an aniline monomer in dilute hydrochloric acid, and stirring and mixing the conductive carbon black and the aniline hydrochloric acid solution for later use, wherein the mark is solution a;
step 2: weighing a certain amount of ammonium persulfate and dissolving the ammonium persulfate in dilute hydrochloric acid, and marking as a solution b;
and 3, step 3: violently stirring the solution a, adding the solution b into the solution a at one time, stirring for a period of time, then assisting with low-temperature ultrasonic synthesis, and then transferring the reaction solution into a thermostat for standing reaction for a period of time;
and 4, step 4: and collecting a product obtained by the reaction, and centrifugally cleaning the product for multiple times by using a mixed solution of ethanol and deionized water to finally obtain a target product.
In step 1, the conductive carbon black is passivated by the following method: the conductive carbon black is concentrated in H2SO4With concentrated HNO3Reacting for 4 hours at 140 ℃ in mixed acid with the volume ratio of 1:3, then filtering and washing to be neutral, and drying.
The concentration of the dilute hydrochloric acid solution used in the step 1 and the step 2 is 1 mol/L; the mass ratio of the conductive carbon black to the aniline monomer is 15: 85; the ratio of the molar weight of aniline monomer to the molar weight of ammonium persulfate was 1: 1.
In step 3, the temperature of low-temperature ultrasound is controlled to be 0-5 ℃ for 30-60 min; the temperature of the constant temperature box is controlled at 0-5 ℃, and the standing reaction time is 180-210 min.
The invention relates to a construction of a self-repairing high-voltage super-electric device, which is a symmetrical super-electric device with a self-repairing function manufactured by the polyaniline/conductive carbon black composite material. Specifically, PANI/SP is used as an active substance, PBI and SHP are used as binders, and SP is used as a conductive agent to manufacture an electrode; using a PBI film as a diaphragm and phosphoric acid as an electrolyte; the two electrodes and the diaphragm are stacked together in a sandwich structure, and the middle of the part coated with the electrode material is covered by a PBI film to assemble a symmetrical device.
The SHP is prepared by the following method: firstly, 41.5g (80% of dibasic acid) of dimer acid and 17g of diethylenetriamine are mixed at 160 ℃, and stirred for 24 hours under the protection of argon; the product was then dissolved in 150ml chloroform and then washed with 150ml deionized water and 75ml methanol to give the SHP precursor; finally, the precursor solution (3ml) was stirred with urea (30mg) at 135 ℃ for 40min to obtain SHP.
The preparation method of the PBI membrane comprises the steps of uniformly spreading a PBI solution with the mass percentage of 5% on a flat glass plate, gently oscillating to enable the PBI solution to automatically flow flatly, and drying at the temperature of 60 ℃ for more than 8 hours to obtain the PBI membrane.
The mass of the electrode material of the symmetrical super-electric device with the self-repairing function is 1.2-2.0 mg.
The invention relates to a construction of a self-repairing high-voltage super-electric device, which is an asymmetric super-electric device with a self-repairing function manufactured by the polyaniline/conductive carbon black composite material. Specifically, PANI/SP is used as a positive electrode, AC is used as a negative electrode, PBI and SHP are used as binders, and SP is used as a conductive agent to manufacture an electrode; using a PBI film as a diaphragm and phosphoric acid as an electrolyte; the two electrodes and the diaphragm are stacked together in a sandwich structure, the middle of the part coated with the electrode material is covered by a PBI film, and an asymmetric device is assembled.
The preparation method of the SHP comprises the steps of firstly mixing 41.5g (80% of dibasic acid) of dimer acid and 17g of diethylenetriamine at 160 ℃, and stirring for 24 hours under the protection of argon; then the product was dissolved in 150ml chloroform and then washed with 150ml deionized water and 75ml methanol to give SHP precursor; finally, the precursor solution (3ml) was stirred with urea (30mg) at 135 ℃ for 40min to obtain SHP.
The preparation method of the PBI membrane comprises the steps of uniformly spreading a PBI solution with the mass percentage of 5% on a flat glass plate, gently oscillating to enable the PBI solution to automatically flow flatly, and drying at the temperature of 60 ℃ for more than 8 hours to obtain the PBI membrane.
The loading ratio of the positive and negative electrode active materials of the device is as follows: m is+：m-＝1.3：1。
The invention relates to a construction of a self-repairing high-voltage super-electric device, which is a super-electric device with a wide voltage window manufactured by the polyaniline/conductive carbon black composite material. Specifically, PANI/SP is used as a positive electrode, AC is used as a negative electrode, PBI and SHP are used as binders, and the electrode is manufactured; taking AC as a negative electrode material, and then adding PVA-H3PO4、PVA-Na2SO4The gel electrolyte thin films are respectively covered on the surfaces of the anode electrode material and the cathode electrode material, and anion membranes are used as diaphragms and stacked together in a sandwich structure to form the asymmetric wide-voltage-window super-electric device.
Said H3PO4The gel is prepared by the following method:
1.8mg of PVA powder were weighed into 60ml of 6M H3PO4In solution inStirring vigorously at 60 deg.C for 2h, standing at 90 deg.C for 1h, naturally cooling to room temperature, and sealing the gel.
The Na is2SO4The gel is prepared by the following method:
dissolving 5g PVA powder in 100ml deionized water under stirring, stirring for 3h at 90 ℃, naturally cooling to room temperature, and slowly dropwise adding 20g 1M Na2SO4And (5) uniformly stirring the solution.
Na2SO4Gel, H3PO4Dripping gel to cover the surface of the electrode material, and assembling a device to improve a voltage window; drying the electrode coated with the gel in an oven at 60 deg.C for 3-5min to obtain a viscous film.
The loading ratio of the positive and negative electrode active materials of the device is as follows: m is a unit of+：m-＝1.5-1：1。
The dimer acid used in the invention is commercially available (brand: Karma, content is more than or equal to 80%, product number P34925-500g), and molecular formula: c36H68O4CAS number: 61788-89-4.
The invention has the beneficial effects that:
1. the raw materials are easy to obtain, the price is low, the cost is low, the method is green and environment-friendly, the requirement on instruments is low, and the operation is simple.
2. The polyaniline super-electric device with the self-repairing performance is manufactured by a simple thought and method, the problem of poor circulation of the current polyaniline super-electric device is solved, and a solution is provided for solving the problem of poor circulation of other conducting polymer devices.
3. The working window of the device is increased to 0-2V by using the double-gel electrolyte, so that the working range of the super capacitor is expanded, and the energy density of the device is effectively improved. The idea of double gel can also be popularized to the manufacture of other devices.
Drawings
FIG. 1 is an SEM image of the PANI/SP composite electrode material, and (a-b) are scanned images at different magnifications.
Fig. 2 is SEM images of PANI/SP composite electrode material before (a) and after (b) cycling.
FIG. 3 is a diagram of electrochemical performance of PANI/SP composite electrode material in a three-electrode system; (a) a CV plot; (b) a CD graph; (c) specific capacities at different current densities; (d) at 2 A.g-1The current density was plotted for 5000 cycles.
Fig. 4 is an SEM image of the PANI/SP composite electrode material without ultrasound-assisted synthesis, (a-b) are scanned images thereof at different magnifications, respectively.
FIG. 5 is a graph of the electrochemical performance of a PANI/SP composite electrode material synthesized using ultrasound assistance versus a PANI/SP composite electrode material synthesized without ultrasound assistance; a) a CV plot; (b) CD graph; (c) the specific capacities of the two composite materials under different current densities; (d) the two composite materials have a weight ratio of 2 A.g-1Current density was plotted against performance for 5000 cycles.
FIG. 6 is a graph of electrochemical performance of a symmetric device with self-healing function made from PANI/SP composite; (a) a CV plot; (b) CD graph; (c) specific capacities at different current densities; (d) in the ratio of 2 A.g-1Current density was plotted for 10000 cycles of cycling performance.
Fig. 7 is SEM images of an electrode sheet having a self-repairing function device before 10000 cycles (a) and after cycles (b).
FIG. 8 is a graph of electrochemical performance of an unshifted SHP symmetric device made from PANI/SP composite versus a self-healing device; (a) a CV plot; (b) CD graph; (c) specific capacities of the two devices under different current densities; (d) two devices at 2A g-1Current density was plotted against 10000 cycles of cycling performance.
FIG. 9 is a graph of electrochemical performance of an asymmetric device with self-healing function made of PANI/SP composite material; (a) a CV plot; (b) CD graph; (c) specific capacities at different current densities; (d) at 2 A.g-1Current density was plotted for 10000 cycles of cycling performance.
FIG. 10 is a graph of electrochemical performance of an unshifted SHP asymmetric device made with PANI/SP composite versus a self-healing device; (a) a CV plot; (b) CD graph; (c) two devices at different current densitiesSpecific capacity; (d) two devices at 2A g-1Current density was plotted against 10000 cycles of cycling performance.
FIG. 11 is a graph of electrochemical performance of a two-gel asymmetric device made with PANI/SP composite; (a) a CV plot; (b) CD graph; (c) specific capacity at different current densities.
FIG. 12 is a graph of electrochemical performance of a single gel asymmetric device made with PANI/SP composite; (a) a CV plot; (b) CD graph; (c) the specific capacity of the single gel and the double gel devices under different current densities.
Detailed Description
The embodiments related to the present invention are specifically illustrated below by examples, which are only limited examples for illustrating the embodiments of the present invention and do not limit the scope of the present invention.
Example 1:
1. preparation of polyaniline/conductive carbon black composite material
Firstly, the conductive carbon black is concentrated in H2SO4With concentrated HNO3Reacting for 4 hours at 140 ℃ in mixed acid with the volume ratio of 1:3, then filtering and washing to be neutral, and drying. Then weighing 340mg of aniline monomer and 60mg of treated conductive carbon black according to the mass ratio of 85:15, dispersing the aniline monomer in 15ml of 1M diluted hydrochloric acid, ultrasonically dispersing the conductive carbon black in 20ml of deionized water, and uniformly stirring and mixing the dispersed aniline monomer and the conductive carbon black together. Then weighing 833mg of ammonium persulfate according to the molar ratio of 1:1, dissolving the ammonium persulfate in 15ml of 1M diluted hydrochloric acid, and adding the dissolved ammonium persulfate into the mixed solution of the aniline monomer and the conductive carbon black at one time. Stirring vigorously for about 1min, placing into an ultrasonic machine, performing ultrasonic-assisted synthesis at low temperature (0-5 deg.C) for about 30min, and standing in a low-temperature incubator (0-5 deg.C) for 210 min. And centrifugally cleaning the obtained solution for three times by using a mixed solution of ethanol and water to finally obtain a product. Dispersing with deionized water, and preparing electrode plate.
2. Three-electrode system electrochemical performance test
The application of the PANI/SP composite electrode material obtained in this embodiment as a supercapacitor electrode material is as follows: assembling a three-electrode system, and compounding PANI/SPThe material was coated on a base graphite paper (1 cm. times.2 cm) with a coating area of 1cm2And (4) drying the substrate for 15min at the temperature of 80 ℃ on a heating table to be used as a working electrode. Using Ag/AgCl as reference electrode and Pt counter electrode as counter electrode, 1M H2SO4The electrochemical performance of the electrode material in a three-electrode system is tested as an electrolyte.
The following conclusions can be drawn from the figures:
the SEM image in fig. 1 clearly shows that PANI fibers were effectively inhibited when ultrasound-assisted synthesis was used and all coated on the surface of the SP.
FIG. 3 shows the PANI/SP composite material tested in a three-electrode system, and the CV curve of FIG. 3(a) shows that the curve is similar under different sweep speeds, which indicates that the material has excellent supercapacitor characteristics and highly reversible reaction. The CD curves in fig. 3(b) all approximate an isosceles triangle and there is no significant voltage drop, indicating that the electrode material is better conductive. FIG. 3(c) specific capacity of electrode material calculated from CD curve at current density of 1Ag-1The specific capacitance of the material is up to 638.9Fg-1At current densities of 1, 2, 5, 10 and 20Ag-1The specific capacity of the electrode is 638.9Fg-1、611.3Fg-1、589.2Fg-1、570.8Fg-1、538.5Fg-1. At 20Ag-1The capacity retention rate was 84.2% at current density, indicating relatively good rate performance. FIG. 3(d) PANI/SP composite obtained by this example at 2Ag-1The specific capacity retention rate of 5000 cycles of the electrode material under constant current charge and discharge is reduced to 65%, which shows that the electrode material has general cycle stability.
Fig. 2(a) (b) are SEM images of the PANI/SP composite before and after cycling, and it is clearly seen that cracks become larger before and after cycling and the corresponding cycle performance is also deteriorated.
Example 2 (comparative): synthesis without ultrasound assistance
1. Preparation of polyaniline/conductive carbon black composite material
Firstly, the conductive carbon black is concentrated in H2SO4With concentrated HNO3Reacting for 4 hours at 140 ℃ in mixed acid with the volume ratio of 1:3, and then filtering and washing untilAnd (5) neutralizing and drying. Then weighing 340mg of aniline monomer and 60mg of treated conductive carbon black according to the mass ratio of 85:15, dispersing the aniline monomer in 15ml of 1M dilute hydrochloric acid, ultrasonically dispersing the conductive carbon black in 20ml of deionized water, and uniformly stirring and mixing the dispersed aniline monomer and the conductive carbon black together. Then weighing 833mg of ammonium persulfate according to the molar ratio of 1:1, dissolving the ammonium persulfate in 15ml of 1M diluted hydrochloric acid, and adding the dissolved ammonium persulfate into the mixed solution of the aniline monomer and the conductive carbon black at one time. Stirring vigorously for about 1min, placing into a low temperature incubator (0-5 deg.C), standing and reacting for 240 min. And centrifugally cleaning the obtained solution for three times by using a mixed solution of ethanol and water to finally obtain a product. Dispersing with deionized water, and preparing electrode plate.
2. Three-electrode system electrochemical performance test
The PANI/SP composite electrode material obtained in this embodiment is applied as a supercapacitor electrode material as follows: assembling a three-electrode system, coating the PANI/SP composite material on a substrate graphite paper (1cm multiplied by 2cm), wherein the coating area is 1cm2And (4) drying the substrate for 15min at the temperature of 80 ℃ on a heating table to be used as a working electrode. Using Ag/AgCl as reference electrode and Pt counter electrode as counter electrode, 1M H2SO4The electrochemical performance of the electrode material in a three-electrode system was tested as an electrolyte.
The following conclusions can be drawn from the figures:
the SEM image in fig. 4 clearly shows that PANI fibers are dispersed around and in the middle of the SP when ultrasound-assisted synthesis is used in place, and is a composite structure of fibrous PANI and PANI-coated SP, which is more randomly distributed compared to ultrasound-assisted synthesis PANI.
FIG. 5 is a graph of electrochemical performance of a PANI/SP composite electrode material synthesized using ultrasound assistance versus a PANI/SP composite electrode material synthesized without ultrasound assistance; FIG. 5(a) the CV curve can be concluded that the curve at different sweep rates shows an approximation, indicating that the material has excellent supercapacitor characteristics and high reversibility; the CD curves in fig. 5(b) all approximate isosceles triangles with no significant voltage drop, indicating that the electrode material is better conductive; it can be seen in fig. 5(c) that the composite properties were significantly higher with the ultrasound-assisted synthesis than without; figure 5(d) clearly shows that 5000 cycles of the composite without ultrasound-assisted synthesis are only 60% compared to 65% for the composite with ultrasound-assisted synthesis. The ultrasonic-assisted synthesis effectively inhibits the formation of PANI long chains, so that PANI is coated on SP, the ion transmission distance is shortened, the performance of the composite material is improved, and the superiority of the ultrasonic-assisted synthesis is reflected.
Example 3: manufacturing method of symmetrical super-electric device with self-repairing function
1. Preparation of polyaniline/conductive carbon black composite material
Same as example 1
2. Preparation of SHP and PBI membranes
The preparation method of SHP is that 41.5g (80% dibasic acid) of dimer acid and 17g of diethylenetriamine are mixed at 160 ℃ and stirred for 24h under the protection of argon. The product was then dissolved in 150ml chloroform and then washed with 150ml deionized water and 75ml methanol to give the SHP precursor. Finally, the precursor solution (3ml) was stirred with urea (30mg) at 135 ℃ for 40min to obtain SHP.
The preparation method of the PBI membrane comprises the steps of uniformly spreading a PBI solution with the mass percentage of 5% on a flat glass plate, gently oscillating to enable the PBI solution to automatically flow flatly, and drying at the temperature of 60 ℃ for more than 8 hours to obtain the PBI membrane.
3. Device fabrication
PANI/SP as an active material, PBI and SHP as a binder, and SP as a conductive agent, in a ratio of PANI/SP: SP: PBI: SHP: 12:3:3:2, and dissolved in a mixed solvent of N-methylpyrrolidone (NMP) and chloroform to prepare an electrode, a PBI membrane was used as a separator, and phosphoric acid was used as an electrolyte. The two electrodes and the diaphragm are stacked together in a sandwich structure, and the middle of the part coated with the electrode material is covered by a PBI film to assemble a symmetrical device.
The following conclusions can be drawn from the figures:
FIG. 6 is a diagram of electrochemical performance of a symmetrical device with self-repairing function, and FIG. 6(a) the CV curve shows that the curve is approximate under different sweep speeds, which shows that the material has excellent super capacitor characteristics and highly reversible reaction; the CD curves in fig. 6(b) all approximate isosceles triangles and there is no significant voltage drop, indicating that the electrode material is better conductive; FIG. 6(c) exhibits its excellent rate performance at low current densities; fig. 6(d) shows that the excellent cycle performance of the self-repairing material has 107% of capacity after 10000 cycles of charging and discharging.
Fig. 7 is SEM images of the electrode sheet of the device having the self-repair function before and after 10000 cycles. It can be clearly seen that the cracks on the electrode sheet are reduced or reduced after 10000 cycles of circulation, so that the effect of the self-repairing polymer is proved, and the corresponding capacity retention rate of 10000 cycles is very good.
Example 4 (comparative): manufacturing method of symmetrical super-electric device without self-repairing polymer (SHP)
1. Preparation of polyaniline/conductive carbon black composite material
Same as example 1
2. Fabrication of PBI membranes
Same as example 2
3. Device fabrication
PANI/SP as an active material, PBI as a binder, and SP as a conductive agent were dissolved in N-methylpyrrolidone (NMP) as a solvent at a ratio of PANI/SP: PBI of 14:3:3 to prepare an electrode, a PBI membrane was used as a separator, and phosphoric acid was used as an electrolyte. The two electrodes and the diaphragm are stacked together in a sandwich structure, the middle of the part coated with the electrode material is covered by a PBI film, and a symmetrical device is assembled.
The following conclusions can be drawn from the figures:
FIG. 8 is a graph of electrochemical performance of an unshifted SHP symmetric device made from PANI/SP composite versus a self-healing device; FIG. 8(a) the CV curve can be found to show that the curve at different sweep rates is similar, indicating that the material has excellent supercapacitor characteristics and high reversibility; the CD curves in fig. 8(b) all approximate isosceles triangles with no significant voltage drop, indicating that the electrode material is better conductive; it can be seen in fig. 8(c) that the performance of the device after the addition of SHP is significantly higher than that of the device without the addition; fig. 8(d) clearly shows that 10000 cycles of the device without the self-repairing polymer are only 68%, and the cycle performance of the self-repairing device is as high as 107%. Fully embodies the superiority of the self-repairing device.
Example 5: manufacturing of asymmetric super-electric device with self-repairing function
1. Preparation of polyaniline/conductive carbon black composite material
Same as example 1
2. Preparation of SHP and PBI film
Same as example 2
3. Device fabrication
The positive electrode is prepared by dissolving PANI/SP as a positive electrode, PBI and SHP as a binder and SP as a conductive agent in a mixed solvent of PANI/SP, PBI, SHP as 12:3:3:2 and N-methylpyrrolidone (NMP) and chloroform. AC as a negative electrode, PBI as a binder, SP as a conductive agent, a negative electrode was prepared using N-methylpyrrolidone (NMP) as a solvent in a ratio of AC: SP: PBI of 80:10:10, PBI film as a separator, and phosphoric acid as an electrolyte. The two electrodes and the diaphragm are stacked together in a sandwich structure, the middle of the part coated with the electrode material is covered by a PBI film, and a symmetrical device is assembled.
The following conclusions can be drawn from the figures:
FIG. 9 is a diagram of electrochemical performance of an asymmetric device with self-repairing function, and FIG. 9(a) a CV curve can be obtained that the curve shows an approximation under different sweep speeds, which shows that the material has excellent super capacitor characteristics and highly reversible reaction; the CD curves in fig. 9(b) all approximate isosceles triangles and there is no significant voltage drop, indicating that the electrode material is better conductive; fig. 9(c) exhibits its superior rate performance at low current densities; fig. 9(d) shows that the excellent cycle performance of the self-repairing material has 108% of capacity after 10000 cycles of charging and discharging.
Example 6 (comparative): asymmetric type super-electric device manufacturing without self-repairing polymer (SHP)
1. Preparation of polyaniline/conductive carbon black composite material
Same as example 1
2. Preparation of SHP and PBI membranes
Same as example 2
3. Device fabrication
The positive electrode is prepared by dissolving PANI/SP as a positive electrode, PBI and SHP as a binder and SP as a conductive agent in a mixed solvent of PANI/SP, PBI, SHP as 12:3:3:2 and N-methylpyrrolidone (NMP) and chloroform. AC as a negative electrode, PBI as a binder, SP as a conductive agent, in a ratio of AC: SP: PBI of 80:10:10, the negative electrode was prepared using N-methylpyrrolidone (NMP) as a solvent, PBI film as a separator, and phosphoric acid as an electrolyte. The two electrodes and the diaphragm are stacked together in a sandwich structure, and the middle of the part coated with the electrode material is covered by a PBI film to assemble a symmetrical device.
The following conclusions can be drawn from the figures:
FIG. 10 is a graph of electrochemical performance of an unshifted symmetrical device made with PANI/SP composite versus a self-healing device; FIG. 10(a) the CV curve can be concluded that the curve at different sweep rates appears similar, indicating that the material has excellent supercapacitor characteristics and highly reversible reactions; the CD curves in fig. 10(b) all approximate isosceles triangles, and the voltage drop is small, indicating that the electrode material is better in conductivity; it can be seen in fig. 10(c) that the performance of the device after the addition of SHP is significantly higher than that of the device without the addition; fig. 10(d) clearly shows that 10000 cycles of the device without the self-repairing polymer are only 79.6%, and the cycle performance of the self-repairing device reaches 108%. The excellent cycle performance of the self-repairing device is fully embodied.
Example 7: construction of wide voltage window double-gel super-electric device
1. Preparation of polyaniline/conductive carbon black composite material
Same as example 1
2、H3PO4，Na2SO4Preparation of the gel
H3PO4The gel is prepared by the following method: 1.8mg of PVA powder are weighed into 60ml of 6M H3PO4Stirring vigorously at 60 deg.C for 2 hr, standing at 90 deg.C for 1 hr, naturally cooling to room temperature, and sealing the gel.
Na2SO4The gel is prepared by the following method: dissolving 5g PVA powder in 100ml deionized water under stirring, stirring for 3h at 90 ℃, naturally cooling to room temperature, and slowly dropwise adding 20g 1M Na2SO4And (5) uniformly stirring the solution.
3. Device fabrication
PANI/SP was used as a positive electrode, PBI and SHP were used as binders, the positive electrode was prepared by dissolving PANI/SP, PBI, SHP in a mixed solvent of N-methylpyrrolidone (NMP) and chloroform at a ratio of 80:5:15, and the negative electrode was prepared by using AC as a negative electrode material, AC: SP, PBI, NMP, 80:10:10, and N-methylpyrrolidone (NMP) as a solvent. Then PVA-H is added3PO4、PVA-Na2SO4The gel electrolyte thin films are respectively covered on the surfaces of the anode electrode material and the cathode electrode material, and anion membranes are used as diaphragms and stacked together in a sandwich structure to form the asymmetric wide-voltage-window super-electric device.
The following conclusions can be drawn from the figures:
fig. 11 shows the electrochemical performance of the double-gel super-electric device, and as can be seen from the CV and CD curves in fig. 11(a), (b), no obvious side reaction is generated when the voltage window is 2.0V, and the voltage is relatively stable. FIG. 11(c) specific capacity calculated based on CD curve at a current density of 1Ag-1When the specific capacity of the double-gel electrolyte device is up to 70.8Fg-1The energy density is as high as 39.3Wh kg-1。
Example 8 (comparative): fabrication of single gel devices
1. Preparation of polyaniline/conductive carbon black composite material
Same as example 1
2、H3PO4Preparation of the gel
Same as example 6
3. Device fabrication
The positive electrode was prepared by using PANI/SP as a positive electrode and PBI and SHP as binders at a ratio of PANI/SP, PBI, SHP of 80:5:15, and dissolved in a mixed solvent of N-methylpyrrolidone (NMP) and chloroform, and the negative electrode was prepared by using AC as a negative electrode material, AC SP, PBI of 80:10:10, and N-methylpyrrolidone (NMP) as a solvent. Then PVA-H is added3PO4Gel electrolyte films are respectively covered on the positive electrodeAnd an anion membrane is used as a diaphragm on the surface of the cathode electrode material, and the anion membrane and the diaphragm are stacked together in a sandwich structure to form the single-gel super-electric device.
The following conclusions can be drawn from the figures:
fig. 12 shows the electrochemical performance of the single-gel super-electric device, and as can be seen from the CV and CD curves in fig. 12(a), (b), no significant side reaction occurs when the voltage window is 1.5V, which is relatively stable. FIG. 12(c) specific capacity calculated based on CD curve at a current density of 1Ag-1When the specific capacity of the single gel electrolyte device reaches 82Fg-1The energy density reaches 25.6Wh kg-1. Much lower than the energy density 39.3Wh kg of the double gel device-1Therefore, the important function of the double-gel device in improving the energy density can be fully embodied.

Claims (10)

1. The preparation method of the polyaniline/conductive carbon black composite material is characterized by comprising the following steps:
step 1: ultrasonically dispersing the passivated conductive carbon black in deionized water, uniformly dispersing an aniline monomer in dilute hydrochloric acid, and stirring and mixing the conductive carbon black and the aniline hydrochloric acid solution for later use, wherein the mark is solution a;
step 2: weighing a certain amount of ammonium persulfate and dissolving the ammonium persulfate in dilute hydrochloric acid, and marking as a solution b;
and 3, step 3: violently stirring the solution a, adding the solution b into the solution a at one time, stirring for a period of time, then assisting with low-temperature ultrasonic synthesis, and then transferring the reaction solution into a thermostat for standing reaction for a period of time;
and 4, step 4: and collecting a product obtained by the reaction, and centrifugally cleaning the product for multiple times by using a mixed solution of ethanol and deionized water to finally obtain a target product.
2. The method of claim 1, wherein:
the mass ratio of the conductive carbon black to the aniline monomer is 15: 85; the ratio of the molar weight of aniline monomer to the molar weight of ammonium persulfate was 1: 1.
In step 3, the temperature of low-temperature ultrasound is controlled to be 0-5 ℃ for 30-60 min; the temperature of the constant temperature box is controlled at 0-5 ℃, and the standing reaction time is 180-210 min.
3. Use of the polyaniline/conductive carbon black composite obtained by the preparation method according to any one of claims 1 to 2, characterized in that: manufacturing a symmetrical super-electric device with a self-repairing function by using the polyaniline/conductive carbon black composite material;
specifically, PANI/SP is used as an active substance, PBI and a self-repairing polymer are used as a binder, and SP is used as a conductive agent to manufacture an electrode; using a PBI film as a diaphragm and phosphoric acid as an electrolyte; two electrodes and a diaphragm are stacked together in a sandwich structure, the middle of the part coated with the electrode material is covered by a PBI film to assemble a symmetrical device, and the electrolyte used by the device is as follows: 6M H3PO4。
4. Use according to claim 3, characterized in that:
the self-repairing polymer is prepared by the following method: firstly, mixing dimer acid and diethylenetriamine at 160 ℃, and stirring for 24 hours under the protection of argon; then dissolving the product in chloroform, and washing with deionized water and methanol to obtain an SHP precursor; and finally, stirring the precursor solution and urea at 135 ℃ for 40min to obtain the self-repairing polymer.
5. Use of the polyaniline/conductive carbon black composite obtained by the preparation method according to any one of claims 1 to 2, characterized in that: manufacturing an asymmetric type super-electric device with a self-repairing function by using the polyaniline/conductive carbon black composite material;
specifically, PANI/SP is used as a positive electrode, AC is used as a negative electrode, PBI and a self-repairing polymer are used as a binder, and SP is used as a conductive agent to manufacture an electrode; using a PBI film as a diaphragm and phosphoric acid as an electrolyte; two electrodes and a diaphragm are stacked together in a sandwich structure, the middle of the part coated with the electrode material is covered by a PBI film, and an asymmetric device is assembled; the electrolyte used by the device is as follows: 6M H3PO4(ii) a Active material for positive and negative electrodes of deviceThe load ratio is as follows: m is+：m-＝1.3：1。
6. Use according to claim 5, characterized in that:
the self-repairing polymer is prepared by the following method: firstly, mixing dimer acid and diethylenetriamine at 160 ℃, and stirring for 24 hours under the protection of argon; then dissolving the product in chloroform, and washing with deionized water and methanol to obtain an SHP precursor; and finally, stirring the precursor solution and urea at 135 ℃ for 40min to obtain the self-repairing polymer.
7. Use of the polyaniline/conductive carbon black composite obtained by the preparation method according to any one of claims 1 to 2, characterized in that: and manufacturing the wide-voltage-window super-electric device by using the polyaniline/conductive carbon black composite material.
Specifically, PANI/SP is used as an anode, AC is used as a cathode, PBI and a self-repairing polymer are used as binders, and an electrode is manufactured; taking AC as a negative electrode material, and then adding PVA-H3PO4、PVA-Na2SO4The gel electrolyte thin films are respectively covered on the surfaces of the anode electrode material and the cathode electrode material, and anion membranes are used as diaphragms and stacked together in a sandwich structure to assemble the asymmetric wide-voltage-window super-electric device; the loading ratio of the positive and negative electrode active materials of the device is as follows: m is a unit of+：m-＝1.5-1：1。
8. Use according to claim 7, characterized in that:
the self-repairing polymer is prepared by the following method: firstly, mixing dimer acid and diethylenetriamine at 160 ℃, and stirring for 24 hours under the protection of argon; then dissolving the product in chloroform, and washing with deionized water and methanol to obtain an SHP precursor; and finally, stirring the precursor solution and urea at 135 ℃ for 40min to obtain the self-repairing polymer.
9. Use according to claim 7, characterized in that:
said H3PO4The gel is prepared by the following method:
1.8mg of PVA powder were weighed into 60ml of 6M H3PO4Stirring the solution at 60 ℃ for 2h, standing the solution at 90 ℃ for 1h, naturally cooling the solution to room temperature, and sealing and storing the gel.
10. Use according to claim 7, characterized in that:
the Na is2SO4The gel is prepared by the following method:
dissolving 5g PVA powder in 100ml deionized water under stirring, stirring at 90 deg.C for 3h, naturally cooling to room temperature, and slowly adding 20g 1M Na dropwise2SO4The solution is stirred evenly.
CN202210385981.0A 2022-04-13 2022-04-13 Preparation of polyaniline/conductive carbon black composite material and construction of self-repairing high-voltage super-electric device Pending CN114709088A (en)

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