CN112216522B - Electrostatic spinning flexible electrode material and preparation method thereof - Google Patents
Electrostatic spinning flexible electrode material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- 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
- H01G11/40—Fibres
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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Abstract
The invention relates to a preparation method of an electrostatic spinning flexible electrode material, which comprises the following steps: adding a carbon nano tube into the cellulose nano whisker suspension to obtain a solution I; mixing polyvinyl alcohol and polyacrylic acid, and dissolving in water to obtain a solution II; mixing the solution I and the solution II to obtain spinning solution; preparing an electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film from the spinning solution by adopting an electrostatic spinning technology; and processing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film by an aniline solution to obtain the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid flexible electrode material. The flexible material has good conductivity, flexibility and stability.
Description
Technical Field
The invention relates to an electrode material and a preparation method thereof, in particular to an electrostatic spinning flexible electrode material and a preparation method thereof.
Background
The flexible super capacitor is a bendable, foldable and twistable super capacitor, integrates the advantages of the traditional capacitor and a battery, and has the advantages of high charge-discharge rate, long cycle life, super-strong stability, safety, environmental protection and the like. As a new energy storage element, a flexible supercapacitor has been widely used in the fields of radio communication, hybrid vehicles, wearable electronic devices, and the like. The super capacitor mainly comprises three parts: electrodes, separators, and electrolytes. The electrode is the most critical component of the super capacitor, and can directly determine the electrical performance of the capacitor, and the existing electrode material comprises carbon nano tubes and polyaniline.
Carbon Nanotube (CNTs) electrode materials not only have excellent capacitance characteristics and stability, but also have high mechanical properties. However, in different processes, the structure, pore size distribution, specific surface area, conductivity and surface functional group difference of CNTs are large, and the CNTs alone cannot ensure that the prepared composite material has good capacitance performance. Polyaniline (PANI) is a structural conductive polymer compound, and a quinoid structure and a benzene structure coexist in a staggered manner, and is commonly called as conductive plastic. The PANI conductive performance is highly controllable, and the PANI electrode material has the advantages of low price, good physical and chemical stability, rapid doping removal capability, good conductive performance and the like, but the electrode material prepared by singly using the PANI has poor relative stability and short service life for a long time.
Electrospinning (Electrospinning) is a special form of atomization of high molecular fluids in electrostatic fields, where a jet of charged polymer solution or melt is normally atomized and split, overcoming the surface tension effect under the action of electrostatic force, and the jet is drawn to a collector and finally solidified into fibers. The one-dimensional nano material with outstanding mechanical property can not only meet the requirement of higher conductivity, but also provide larger relative ratio surface area and higher pore volume for active substances.
Cellulose is a green renewable high molecular compound and has wide sources. After the nano-scale cellulose nano-gel is prepared, the nano-scale cellulose nano-gel not only has the advantages of light weight, large specific surface area, large length-diameter ratio, high mechanical strength, large Young modulus and the like, but also can be stably dispersed in a solvent system for a long time to form stable and uniform transparent nano-cellulose gel. Wherein, the Cellulose nano whiskers (CNCs) are rod-shaped or granular, the length-diameter ratio is about 16.6, and the strength is very high.
Therefore, the flexible material obtained by combining the electrostatic spinning technology, the carbon nano tube, the polyaniline and the cellulose has wide application prospect.
Disclosure of Invention
The invention aims to provide a flexible electrode material, which takes polyvinyl alcohol and polyacrylic acid as an electrostatic spinning polymer matrix and adopts an electrostatic spinning technology to cooperate with an electrode material carbon nano tube to form the flexible electrode material.
The technical scheme adopted by the invention is as follows: the preparation method of the electrostatic spinning flexible electrode material comprises the following steps
S01, adding the carbon nano tube into the cellulose nano whisker suspension to obtain a solution I; mixing polyvinyl alcohol and polyacrylic acid, and dissolving in water to obtain a solution II; mixing the solution I and the solution II to obtain spinning solution;
s02, preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film from the spinning solution by adopting an electrostatic spinning technology as a flexible electrode material.
In order to further improve the electrical property, the mechanical property and the thermal stability of the flexible electrode material, the method further comprises a step S03 of processing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conducting film by an aniline solution to obtain the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid flexible electrode material as the further improved flexible electrode material.
Further, the preparation method of the cellulose nano whisker suspension liquid comprises the following steps
(1) Adding bleached wood pulp fiber into a sulfuric acid solution for acidolysis reaction;
(2) adding deionized water to terminate the acidolysis reaction to obtain a first suspension, filtering the first suspension, re-dispersing the first suspension in the deionized water, transferring the mixture into a dialysis bag, and dialyzing the mixture until the pH value is neutral to obtain a second suspension;
(3) and adding deionized water into the suspension II for dilution, and performing ultrasonic treatment to prepare the cellulose nanowhisker suspension.
Further, the mass concentration of the sulfuric acid solution is 55-75%, and the acidolysis reaction time is 50-70 minutes.
Further, the preparation method of the solution I comprises the following steps: adding the carbon nano tube into the cellulose nano whisker suspension, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nano tube-cellulose nano whisker conductive nano composite solution.
Further, the mass ratio of the carbon nano tube to the solute in the second solution is 0.5: 100-2: 100; the mass ratio of the cellulose nanowhiskers in the cellulose nanowhisker suspension to the solute in the solution II is 6: 100-10:100.
Further, the mass ratio of the polyacrylic acid to the polyvinyl alcohol is 5:10-15:10, solute polyacrylic acid and polyvinyl alcohol in the second solution are dissolved, and the concentration of the solute in the second solution is 6.0wt% -10.0 wt%.
Further, step S02 is specifically
(1) Injecting the spinning solution into an injector, applying a voltage of 19-23kV between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) connecting a positive voltage with the needle head, and connecting a negative voltage with the roller collector to prepare the electrostatic spinning carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic fiber conductive prefabricated film;
(3) placing the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at the temperature of 130-150 ℃ for esterification and crosslinking reaction to obtain an electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film;
further, step S03 is specifically
(1) Soaking the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film in an ethanol solution of aniline;
(2) and transferring the soaked electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film into a hydrochloric acid solution of ammonium persulfate to carry out an oxidation reaction, and obtaining the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film after the oxidation reaction.
The invention also provides an electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid flexible electrode material prepared by the preparation method.
The beneficial effects produced by the invention comprise: (1) the hydrophilic biodegradable non-toxic high molecular polymer is selected to play a role in protecting the environment;
(2) cellulose nanowhiskers extracted from natural cellulose are used as a dispersing agent of the carbon nano tube, the carbon nano tube is carried to form a uniform and stable nano conductive compound, a nano enhanced network and an electron transmission network are constructed in the composite membrane, the formation of a conductive path of a fiber conductive membrane is facilitated, and the mechanical property and the thermal stability of the fiber conductive membrane are doubly enhanced;
(3) polyvinyl alcohol (PVA) can be completely dissolved in water at a high temperature of 80 ℃, the solution is non-toxic, has excellent chemical stability, cohesiveness and biocompatibility, simultaneously has good processability and film forming property, can be biodegraded, and polyacrylic acid (PAA) is a water-soluble organic polymer and has good mechanical property and biocompatibility. At high temperature, PAA and PVA can generate esterification crosslinking reaction to form ester substances, so that the hydrophobic property and the mechanical property of the fiber conducting film are improved;
(4) the polyaniline is polymerized in situ on the surface of the crosslinked fiber conducting film by adopting an in-situ polymerization method, so that the electrical property of the polyaniline is exerted to the maximum extent, and the mechanical property and the thermal stability of the fiber conducting film are improved;
(5) the polyaniline has good conductivity, the carbon nano tube has excellent cycling stability, and the two conductive materials are added simultaneously, so that the advantages are complementary, and the preparation of the flexible electrode material with excellent conductivity and stable cycling is facilitated;
(6) the flexible electrode material prepared by the invention has good foldable, bendable and twistable capacity.
Drawings
Fig. 1 is a water contact angle graph of electrospun carbon nanotubes/cellulose nanowhiskers/polyvinyl alcohol/polyacrylic acid fiber conductive films of examples 1-6;
FIG. 2 is a stress-strain curve of the electrospun carbon nanotubes/cellulose nanowhiskers/polyvinyl alcohol/polyacrylic fiber conductive films of examples 1-6;
fig. 3 is a graph of the conductivity of the electrospun polyaniline/carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic fiber conductive films of examples 7-10;
FIG. 4 is a graph of the conductivity of the electro-spun polyaniline/carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid fiber conductive film of example 8 under different deformation conditions;
FIG. 5 is a GCD plot of the electrospun polyaniline/carbon nanotubes/cellulose nanowhiskers/polyvinyl alcohol/polyacrylic fiber conductive films of examples 7-10;
fig. 6 is a graph of the cycling stability of electrospun polyaniline/carbon nanotubes/cellulose nanowhiskers/polyvinyl alcohol/polyacrylic fiber conductive films of examples 7-10.
Detailed Description
The present invention is explained in further detail below with reference to the drawings and the embodiments, but it should be understood that the scope of the present invention is not limited to the embodiments.
Example 1
(1) adding 5g of bleached wood pulp fiber dried in advance into 100g of sulfuric acid with the mass fraction of 55%, and performing magnetic stirring acid hydrolysis at 40 ℃ for 50 minutes;
(2) adding deionized water to terminate the acidolysis reaction to obtain a first suspension, filtering the first suspension to obtain cellulose, re-dispersing the cellulose in the deionized water, and then transferring the cellulose into a dialysis bag to dialyze until the pH value is neutral to obtain a second suspension;
(3) and taking the second suspension, adding deionized water for dilution, carrying out ultrasonic treatment for 75 minutes under the power of 900w to prepare the cellulose nano whisker suspension, and refrigerating for later use.
(1) dissolving polyvinyl alcohol in water bath at 90 ℃ for 3.5h until the polyvinyl alcohol is completely dissolved in water, preparing a mixed solution with water by using polyacrylic acid and polyvinyl alcohol as solutes, wherein the mass ratio of the polyacrylic acid to the polyvinyl alcohol in the mixed solution is 1: 2, solute concentration is 6.0 wt%;
(2) adding carbon nano tubes into the cellulose nano whisker suspension, wherein the mass of the carbon nano tubes is 0.5wt% of the mass of the polyvinyl alcohol-polyacrylic acid solid, and the mass of the cellulose nano whiskers is 6.0wt% of the mass of the polyvinyl alcohol-polyacrylic acid solid, mixing, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nano tube-cellulose nano whisker conductive nano composite solution;
(3) adding the carbon nano tube-cellulose nano whisker conductive nano composite solution into a prepared mixed solution of polyvinyl alcohol and polyacrylic acid, stirring and carrying out ultrasonic treatment until a uniform and stable spinning solution is formed;
step 3, preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, wherein the specific method comprises the following steps:
(1) injecting the spinning solution into a 1.0mL injector, applying a voltage of 19kV between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) the positive voltage is connected to the needle and the negative voltage is connected to the roller collector. Keeping the propelling speed of the pump at 1.0mL/h and the rotating speed of the roller collector at 1200r/min, and preparing the electrostatic spinning carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film;
(3) and (3) placing the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at the temperature of 130 ℃ for esterification and crosslinking reaction for 2 hours to obtain the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, namely the electrostatic spinning flexible electrode material 1.
Example 2
(1) adding 10g of bleached wood pulp fiber dried in advance into 200g of sulfuric acid with the mass fraction of 65%, and performing magnetic stirring acid hydrolysis at 45 ℃ for 60 minutes;
(2) adding deionized water to terminate acidolysis reaction, filtering the obtained suspension, redispersing in deionized water, and transferring into a dialysis bag for dialysis until the pH value is neutral;
(3) and (3) taking the suspension, adding deionized water for dilution, carrying out ultrasonic treatment for 90 minutes under the power of 1000w to prepare the cellulose nano whisker suspension, and refrigerating for later use.
(1) dissolving polyvinyl alcohol at 90 ℃ water bath temperature for 4h until the polyvinyl alcohol is completely dissolved, wherein the weight ratio of polyacrylic acid to polyvinyl alcohol is 4: 5, preparing a mixed solution of polyvinyl alcohol and polyacrylic acid, and keeping the concentration of relative water to be 8.0 wt%;
(2) adding carbon nanotubes accounting for 1.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid into cellulose nanowhisker suspension accounting for 8.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nanotube-cellulose nanowhisker conductive nanocomposite solution;
(3) adding the carbon nano tube-cellulose nano whisker conductive nano composite solution into a prepared mixed solution of polyvinyl alcohol and polyacrylic acid, stirring and performing ultrasonic treatment until a uniform and stable spinning solution is formed;
step 3, preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, wherein the specific method comprises the following steps:
(1) injecting the spinning solution into a 1.0mL injector, applying 21kV voltage between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) the positive voltage is connected with the needle head, and the negative voltage is connected with the roller collector. Keeping the propelling speed of the pump at 1.0mL/h and the rotating speed of the roller collector at 1200r/min, and preparing the electrostatic spinning carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film;
(3) and (3) placing the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at 140 ℃ for esterification and crosslinking reaction for 2 hours to obtain the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, namely the electrostatic spinning flexible electrode material 2.
Example 3
(1) adding 10g of bleached wood pulp fiber dried in advance into 200g of sulfuric acid with the mass fraction of 64%, and performing magnetic stirring acid hydrolysis at 45 ℃ for 60 minutes;
(2) adding deionized water to terminate acidolysis reaction, filtering the obtained suspension, redispersing in deionized water, and transferring into a dialysis bag for dialysis until the pH value is neutral;
(3) and (3) taking the suspension, adding deionized water for dilution, carrying out ultrasonic treatment for 90 minutes under the power of 1000w to prepare the cellulose nano whisker suspension, and refrigerating for later use.
(1) dissolving polyvinyl alcohol for 4 hours at the water bath temperature of 90 ℃ until the polyvinyl alcohol is completely dissolved, wherein the weight ratio of polyacrylic acid to polyvinyl alcohol 1: 1, preparing a mixed solution of polyvinyl alcohol and polyacrylic acid, and keeping the concentration of relative water to be 8.0 wt%;
(2) adding carbon nanotubes accounting for 1.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid into cellulose nanowhisker suspension accounting for 8.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nanotube-cellulose nanowhisker conductive nanocomposite solution;
(3) adding the carbon nano tube-cellulose nano whisker conductive nano composite solution into a prepared mixed solution of polyvinyl alcohol and polyacrylic acid, stirring and performing ultrasonic treatment until a uniform and stable spinning solution is formed;
step 3, preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, wherein the specific method comprises the following steps:
(1) injecting the spinning solution into a 1.0mL injector, applying 21kV voltage between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) the positive voltage is connected with the needle head, and the negative voltage is connected with the roller collector. Keeping the propelling speed of the pump at 1.0mL/h and the rotating speed of the roller collector at 1200r/min, and preparing the electrostatic spinning carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film;
(3) and (3) placing the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at 140 ℃ for esterification and crosslinking reaction for 2 hours to obtain the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, namely the electrostatic spinning flexible electrode material 3.
Example 4
(1) adding 5g of bleached wood pulp fiber dried in advance into 100g of sulfuric acid with the mass fraction of 65%, and performing magnetic stirring acid hydrolysis at the temperature of 45 ℃ for 60 minutes;
(2) adding deionized water to terminate acidolysis reaction, filtering the obtained suspension, redispersing in deionized water, and transferring into a dialysis bag for dialysis until the pH value is neutral;
(3) and (3) taking the suspension, adding deionized water for dilution, carrying out ultrasonic treatment for 75 minutes under the power of 1000w to prepare the cellulose nano whisker suspension, and refrigerating for later use.
(1) dissolving polyvinyl alcohol for 4 hours at the water bath temperature of 90 ℃ until the polyvinyl alcohol is completely dissolved, wherein the weight ratio of polyacrylic acid to polyvinyl alcohol 6: 5, preparing a mixed solution of polyvinyl alcohol and polyacrylic acid, and keeping the concentration of relative water to be 10.0 wt%;
(2) adding carbon nanotubes accounting for 2.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid into cellulose nanowhisker suspension accounting for 10.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nanotube-cellulose nanowhisker conductive nanocomposite solution;
(3) adding the carbon nano tube-cellulose nano whisker conductive nano composite solution into a prepared mixed solution of polyvinyl alcohol and polyacrylic acid, stirring and performing ultrasonic treatment until a uniform and stable spinning solution is formed;
step 3, preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, wherein the specific method comprises the following steps:
(1) injecting the spinning solution into a 1.0mL injector, applying 21kV voltage between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) the positive voltage is connected with the needle head, and the negative voltage is connected with the roller collector. Keeping the propelling speed of the pump at 1.0mL/h and the rotating speed of the roller collector at 1200r/min, and preparing the electrostatic spinning carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film;
(3) and (3) placing the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at the temperature of 150 ℃ for esterification and crosslinking reaction for 2 hours to obtain the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, namely the electrostatic spinning flexible electrode material 4.
Example 5
(1) adding 15g of bleached wood pulp fiber dried in advance into 300g of sulfuric acid with the mass fraction of 75%, and performing magnetic stirring acid hydrolysis at the temperature of 50 ℃ for 70 minutes;
(2) adding deionized water to terminate acidolysis reaction, filtering the obtained suspension, redispersing in deionized water, and transferring into a dialysis bag for dialysis until the pH value is neutral;
(3) and (3) taking the suspension, adding deionized water for dilution, carrying out ultrasonic treatment for 105 minutes at 1100w of power to prepare the cellulose nano whisker suspension, and refrigerating for later use.
(1) dissolving polyvinyl alcohol at 90 ℃ water bath temperature for 4.5h until the polyvinyl alcohol is completely dissolved, wherein the weight ratio of polyacrylic acid to polyvinyl alcohol 3: 2, preparing a mixed solution of polyvinyl alcohol and polyacrylic acid, and keeping the concentration of the relative water to be 8.0 wt%;
(2) adding carbon nanotubes accounting for 1.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid into cellulose nanowhisker suspension accounting for 8.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nanotube-cellulose nanowhisker conductive nanocomposite solution;
(3) adding the carbon nano tube-cellulose nano whisker conductive nano composite solution into a prepared mixed solution of polyvinyl alcohol and polyacrylic acid, stirring and performing ultrasonic treatment until a uniform and stable spinning solution is formed;
step 3, preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, wherein the specific method comprises the following steps:
(1) injecting the spinning solution into a 1.0mL injector, applying a voltage of 23kV between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) the positive voltage is connected with the needle head, and the negative voltage is connected with the roller collector. Keeping the propelling speed of the pump at 1.0mL/h and the rotating speed of the roller collector at 1200r/min, and preparing the electrostatic spinning carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film;
(3) and (3) placing the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at the temperature of 150 ℃ for esterification and crosslinking reaction for 2 hours to obtain the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, namely the electrostatic spinning flexible electrode material 5.
Example 6
(1) adding 10g of bleached wood pulp fiber dried in advance into 200g of sulfuric acid with the mass fraction of 64%, and performing magnetic stirring acid hydrolysis at 45 ℃ for 60 minutes;
(2) adding deionized water to terminate acidolysis reaction, filtering the obtained suspension, dispersing in deionized water again, transferring to a dialysis bag, and dialyzing to neutral pH value;
(3) and (3) taking the suspension, adding deionized water for dilution, carrying out ultrasonic treatment for 90 minutes under the power of 1000w to prepare the cellulose nano whisker suspension, and refrigerating for later use.
(1) dissolving polyvinyl alcohol for 4 hours at the water bath temperature of 90 ℃ until the polyvinyl alcohol is completely dissolved, wherein the weight ratio of polyacrylic acid to polyvinyl alcohol 1: 1, preparing a mixed solution of polyvinyl alcohol and polyacrylic acid, and keeping the concentration of relative water to be 8.0 wt%;
(2) adding carbon nanotubes accounting for 1.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid into cellulose nanowhisker suspension accounting for 8.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nanotube-cellulose nanowhisker conductive nanocomposite solution;
(3) adding the carbon nano tube-cellulose nano whisker conductive nano composite solution into a prepared mixed solution of polyvinyl alcohol and polyacrylic acid, stirring and performing ultrasonic treatment until a uniform and stable spinning solution is formed;
step 3, preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, wherein the specific method comprises the following steps:
(1) injecting the spinning solution into a 1.0mL injector, applying 21kV voltage between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) the positive voltage is connected with the needle head, and the negative voltage is connected with the roller collector. Keeping the propelling speed of the pump at 1.0mL/h and the rotating speed of the roller collector at 1200r/min, and preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film to obtain the flexible electrode material 6.
Example 7
(1) adding 10g of bleached wood pulp fiber dried in advance into 200g of sulfuric acid with the mass fraction of 65%, and performing magnetic stirring acid hydrolysis at 45 ℃ for 90 minutes;
(2) adding deionized water to terminate acidolysis reaction, filtering the obtained suspension, redispersing in deionized water, and transferring into a dialysis bag for dialysis until the pH value is neutral;
(3) and (3) taking the suspension, adding deionized water for dilution, performing ultrasonic treatment for 100 minutes at 1100w of power to prepare the cellulose nano whisker suspension, and refrigerating for later use.
(1) dissolving polyvinyl alcohol for 4 hours at the water bath temperature of 90 ℃ until the polyvinyl alcohol is completely dissolved, wherein the weight ratio of polyacrylic acid to polyvinyl alcohol 1: 1, preparing a mixed solution of polyvinyl alcohol and polyacrylic acid, and keeping the concentration of relative water to be 8.0 wt%;
(2) adding carbon nanotubes accounting for 1.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid into cellulose nanowhisker suspension accounting for 8.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nanotube-cellulose nanowhisker conductive nanocomposite solution;
(3) adding the carbon nano tube-cellulose nano whisker conductive nano composite solution into a prepared mixed solution of polyvinyl alcohol and polyacrylic acid, stirring and performing ultrasonic treatment until a uniform and stable spinning solution is formed;
step 3, preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, wherein the specific method comprises the following steps:
(1) injecting the spinning solution into a 1.0mL injector, applying 21kV voltage between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) the positive voltage is connected with the needle head, and the negative voltage is connected with the roller collector. Keeping the propelling speed of the pump at 1.0mL/h and the rotating speed of the roller collector at 1200r/min, and preparing the electrostatic spinning carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film;
(3) putting the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at 140 ℃ for esterification and crosslinking reaction for 2 hours;
step 4, preparing the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic fiber conductive film, wherein the specific method comprises the following steps:
(1) soaking the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film in an ethanol solution of aniline with a certain concentration;
(2) and transferring the fiber conducting film to a hydrochloric acid solution with certain ammonium persulfate solubility, and carrying out oxidation reaction in an ice-water bath for 3h to obtain the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conducting film, thereby preparing the flexible electrode material 7.
Example 8
(1) adding 10g of bleached wood pulp fiber dried in advance into 200g of sulfuric acid with the mass fraction of 65%, and performing magnetic stirring acid hydrolysis at 45 ℃ for 90 minutes;
(2) adding deionized water to terminate acidolysis reaction, filtering the obtained suspension, redispersing in deionized water, and transferring into a dialysis bag for dialysis until the pH value is neutral;
(3) and (3) taking the suspension, adding deionized water for dilution, carrying out ultrasonic treatment for 90 minutes under the power of 1000w to prepare the cellulose nano whisker suspension, and refrigerating for later use.
(1) dissolving polyvinyl alcohol for 4 hours at the water bath temperature of 90 ℃ until the polyvinyl alcohol is completely dissolved, wherein the weight ratio of polyacrylic acid to polyvinyl alcohol 1: 1, preparing a mixed solution of polyvinyl alcohol and polyacrylic acid, and keeping the concentration of relative water to be 8.0 wt%;
(2) adding carbon nanotubes accounting for 1.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid into cellulose nanowhisker suspension accounting for 8.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nanotube-cellulose nanowhisker conductive nanocomposite solution;
(3) adding the carbon nano tube-cellulose nano whisker conductive nano composite solution into a prepared mixed solution of polyvinyl alcohol and polyacrylic acid, stirring and performing ultrasonic treatment until a uniform and stable spinning solution is formed;
step 3, preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, wherein the specific method comprises the following steps:
(1) injecting the spinning solution into a 1.0mL injector, applying 21kV voltage between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) the positive voltage is connected to the needle and the negative voltage is connected to the roller collector. Keeping the propelling speed of the pump at 1.0mL/h and the rotating speed of the roller collector at 1200r/min, and preparing the electrostatic spinning carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film;
(3) putting the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at 140 ℃ for esterification and crosslinking reaction for 2 hours;
step 4, preparing the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic fiber conductive film, wherein the specific method comprises the following steps:
(1) soaking the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film in an ethanol solution of aniline with a certain concentration;
(2) transferring the fiber conducting film to a hydrochloric acid solution with certain ammonium persulfate solubility, and carrying out oxidation reaction in an ice-water bath for 6h to obtain an electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conducting film, thereby preparing a flexible electrode material 8
Example 9
(1) adding 10g of bleached wood pulp fiber dried in advance into 200g of sulfuric acid with the mass fraction of 65%, and performing magnetic stirring acid hydrolysis at 45 ℃ for 90 minutes;
(2) adding deionized water to terminate acidolysis reaction, filtering the obtained suspension, redispersing in deionized water, and transferring into a dialysis bag for dialysis until the pH value is neutral;
(3) and (3) taking the suspension, adding deionized water for dilution, performing ultrasonic treatment for 100 minutes at the power of 1000w to prepare the cellulose nano whisker suspension, and refrigerating for later use.
(1) dissolving polyvinyl alcohol for 4 hours at the water bath temperature of 90 ℃ until the polyvinyl alcohol is completely dissolved, wherein the weight ratio of polyacrylic acid to polyvinyl alcohol 1: 1, preparing a mixed solution of polyvinyl alcohol and polyacrylic acid, and keeping the concentration of relative water to be 8.0 wt%;
(2) adding carbon nanotubes accounting for 1.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid into cellulose nanowhisker suspension accounting for 8.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nanotube-cellulose nanowhisker conductive nanocomposite solution;
(3) adding the carbon nano tube-cellulose nano whisker conductive nano composite solution into a prepared mixed solution of polyvinyl alcohol and polyacrylic acid, stirring and performing ultrasonic treatment until a uniform and stable spinning solution is formed;
step 3, preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, wherein the specific method comprises the following steps:
(1) injecting the spinning solution into a 1.0mL injector, applying 21kV voltage between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) the positive voltage is connected with the needle head, and the negative voltage is connected with the roller collector. Keeping the propelling speed of the pump at 1.0mL/h and the rotating speed of the roller collector at 1200r/min, and preparing the electrostatic spinning carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film;
(3) putting the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at 140 ℃ for esterification and crosslinking reaction for 2 hours;
step 4, preparing the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic fiber conductive film, wherein the specific method comprises the following steps:
(1) soaking the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film in an ethanol solution of aniline with a certain concentration;
(2) and transferring the fiber conducting film to a hydrochloric acid solution with certain ammonium persulfate solubility, and carrying out oxidation reaction in an ice-water bath for 9 hours to obtain the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conducting film, thereby preparing the flexible electrode material 9.
Example 10
(1) adding 10g of bleached wood pulp fiber dried in advance into 200g of sulfuric acid with the mass fraction of 65%, and performing magnetic stirring acid hydrolysis at 45 ℃ for 90 minutes;
(2) adding deionized water to terminate acidolysis reaction, filtering the obtained suspension, redispersing in deionized water, and transferring into a dialysis bag for dialysis until the pH value is neutral;
(3) and (3) taking the suspension, adding deionized water for dilution, performing ultrasonic treatment for 100 minutes at the power of 1000w to prepare the cellulose nano whisker suspension, and refrigerating for later use.
(1) dissolving polyvinyl alcohol for 4 hours at the water bath temperature of 90 ℃ until the polyvinyl alcohol is completely dissolved, wherein the weight ratio of polyacrylic acid to polyvinyl alcohol 1: 1, preparing a mixed solution of polyvinyl alcohol and polyacrylic acid, and keeping the concentration of relative water to be 8.0 wt%;
(2) adding carbon nanotubes accounting for 1.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid into cellulose nanowhisker suspension accounting for 8.0wt% of the solid mass of the polyvinyl alcohol-polyacrylic acid, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nanotube-cellulose nanowhisker conductive nanocomposite solution;
(3) adding the carbon nano tube-cellulose nano whisker conductive nano composite solution into a prepared mixed solution of polyvinyl alcohol and polyacrylic acid, stirring and performing ultrasonic treatment until a uniform and stable spinning solution is formed;
step 3, preparing the electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film, wherein the specific method comprises the following steps:
(1) injecting the spinning solution into a 1.0mL injector, applying 21kV voltage between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) the positive voltage is connected with the needle head, and the negative voltage is connected with the roller collector. Keeping the propelling speed of the pump at 1.0mL/h and the rotating speed of a roller collector at 1200r/min, and preparing an electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film;
(3) putting the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at 140 ℃ for esterification and crosslinking reaction for 2 hours;
step 4, preparing the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic fiber conductive film, wherein the specific method comprises the following steps:
(1) soaking the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive film in an ethanol solution of aniline with a certain concentration;
(2) and transferring the fiber conducting film to a hydrochloric acid solution with certain ammonium persulfate solubility, and carrying out oxidation reaction in an ice-water bath for a certain time of 12 hours to obtain the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conducting film, so as to prepare the flexible electrode material 10.
Referring to FIGS. 1 and 2, A1-A5Sequentially corresponding to the flexible electrode materials 1-5, A0Corresponding to the flexible electrode material 6, as can be seen from fig. 1 and 2, after the polyvinyl alcohol and the polyacrylic acid are subjected to a crosslinking reaction, the hydrophobic property and the mechanical property of the electrostatic spinning carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid fiber conductive film are obviously enhanced. Meanwhile, when the polyvinyl alcohol and polyacrylic acid are mixed in a ratio of 1: 1, the prepared electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic fiber conductive film has hydrophobicity (contact angle is 54.8)O) And the mechanical properties (tensile strength 47.80 +/-0.42 MPa, elastic modulus 92.63 +/-0.17 MPa) are optimal.
As shown in FIG. 3, sample A3-3，A3-6，A3-9，A312 correspond in turn to the flexible electrode materials 7 to 10, as can be seen from FIG. 3, sample A3-3，A3-6，A3-9，A3The electrical conductivity of-12 is respectively 0.22 +/-0.004S/m, 0.32 +/-0.003S/m, 0.319 +/-0.004S/m and 0.315 +/-0.003S/m, and the electrical conductivity of the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid flexible electrode material is increased and then reduced along with the increase of the polymerization time of polyaniline, which indicates that a continuous conductive network can be formed inside a conductive film when the polyaniline is polymerized for 6 hours.
Fig. 4 is a detection result of the flexible electrode material 8 prepared in example 8, and it can be seen from fig. 4 that, under different mechanical deformations, the brightness of the small bulb connected by the electrospun polyaniline/carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid flexible electrode material is almost unchanged, which indicates that the fiber conductive film has good flexibility, and the conductivity remains almost unchanged at 0.32 ± 0.003S/m after undergoing different mechanical deformations.
As shown in FIG. 5, sample A3-3，A3-6，A3-9，A3-12 corresponding in sequence to the flexible electrode material 7-10; a. the3-3，A3-6，A3-9，A3The-12 specific capacitances correspond to 119.7F/g, 164.6F/g, 129.6F/g and 102.3F/g respectively, and as can be seen from FIG. 5, the electrospun polyaniline/carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid flexible electrode material has higher specific capacitance and the specific capacitance is the best (164.6F/g) when polyaniline is polymerized for 6 h.
As can be seen from fig. 6, the electrostatic spinning polyaniline/carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic acid flexible electrode material has good cycle stability, and is optimal when polyaniline is polymerized for 6 hours, and after 2000 charge-discharge cycles, the specific capacitance retention rate can still reach 91.14%.
The technical means disclosed in the invention scheme are not limited to the technical means disclosed in the above embodiments, but also include the technical scheme formed by any combination of the above technical features. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.
Claims (2)
1. A preparation method of an electrostatic spinning flexible electrode material is characterized by comprising the following steps: the method comprises the following steps:
s01, adding the carbon nano tube into the cellulose nano whisker suspension to obtain a solution I; mixing polyvinyl alcohol and polyacrylic acid, and dissolving in water to obtain a solution II; mixing the solution I and the solution II to obtain spinning solution; the preparation method of the solution I comprises the following steps: adding carbon nano tubes into the cellulose nano whisker suspension, stirring and carrying out ultrasonic treatment to form uniform and stable carbon nano tube-cellulose nano whisker conductive nano composite solution; the mass ratio of the carbon nano tube to the solute in the solution II is 0.5: 100-2: 100; the mass ratio of the cellulose nanowhiskers in the cellulose nanowhisker suspension to the solute in the solution II is 6: 100-10: 100; the mass ratio of the polyacrylic acid to the polyvinyl alcohol is 5:10-15:10, wherein the solute in the second solution is polyacrylic acid and polyvinyl alcohol, and the concentration of the solute in the second solution is 6.0wt% -10.0 wt%;
the preparation method of the cellulose nano whisker suspension liquid comprises the following steps:
(1) adding bleached wood pulp fiber into a sulfuric acid solution for acidolysis reaction; the mass concentration of the sulfuric acid solution is 55-75%, and the acidolysis reaction time is 50-70 minutes;
(2) adding deionized water to terminate acidolysis reaction to obtain a first suspension, filtering the first suspension, dispersing the first suspension in the deionized water again, transferring the mixture into a dialysis bag, and dialyzing the mixture until the pH value is neutral to obtain a second suspension;
(3) adding deionized water into the suspension II for dilution, and performing ultrasonic treatment to prepare a cellulose nanowhisker suspension;
s02, preparing an electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film from the spinning solution by adopting an electrostatic spinning technology; placing the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at the temperature of 130-150 ℃ for esterification and crosslinking reaction to prepare a flexible electrode material;
the method specifically comprises the following steps:
(1) injecting the spinning solution into an injector, applying a voltage of 19-23kV between a roller receiver and a needle head, and controlling the receiving distance to be 10-15 cm;
(2) connecting a positive voltage with the needle head, and connecting a negative voltage with the roller collector to prepare the electrostatic spinning carbon nanotube/cellulose nanowhisker/polyvinyl alcohol/polyacrylic fiber conductive prefabricated film;
(3) placing the obtained electrostatic spinning carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid fiber conductive prefabricated film in a vacuum oven at the temperature of 130-150 ℃ for esterification and crosslinking reaction to obtain the flexible electrode material;
s03, treating the flexible electrode material through aniline solution;
the method specifically comprises the following steps:
(1) soaking the obtained flexible electrode material in an ethanol solution of aniline;
(2) and transferring the soaked flexible electrode material into a hydrochloric acid solution of ammonium persulfate to carry out an oxidation reaction, and obtaining the electrostatic spinning polyaniline/carbon nano tube/cellulose nano whisker/polyvinyl alcohol/polyacrylic acid flexible electrode material after the oxidation reaction.
2. An electrospun flexible electrode material prepared according to the preparation method of claim 1.
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