CN107746572B - Preparation method of hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel - Google Patents
Preparation method of hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel Download PDFInfo
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Abstract
The invention discloses a preparation method of hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel, which comprises the following steps: firstly, dissolving sodium alginate, an acidic doping agent and N-methylaniline in deionized water to obtain a solution A; dissolving an oxidant and lignosulfonate in deionized water to obtain a solution B; thirdly, uniformly mixing the solution A and the solution B, and then standing for reaction; and fourthly, purifying and balancing the mixture in deionized water, and finally filtering the mixture to obtain the purified PNMA/lignosulfonic acid hybrid hydrogel. The method is simple, the reaction condition is mild, the requirement on the performance of equipment is low, and the PNMA/lignosulfonic acid hybrid hydrogel can be obtained only by virtue of the supramolecular self-assembly behavior of a reaction system. The obtained hybrid hydrogel has a nanoscale hierarchical porous structure, shows higher specific capacitance and cycle life, is particularly suitable for energy storage electrode materials, and has wide application prospects in the fields of sensing, catalysis, heavy metal ion adsorption and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of conductive polymer-based new energy materials, and particularly relates to a preparation method of hierarchical porous PNMA/lignosulfonic acid hybrid hydrogel.
Background
As an important electrochemical energy storage material, the conductive polymer has the advantages of low cost, small environmental pollution, high charge density, wide potential window, adjustable redox activity and the like, and is paid much attention in the research field of electrode materials of super capacitors. Among conductive polymers, polyaniline is gradually the most widely studied electrode material due to its easy preparation, high doping ability, good conductivity, high electrochemical activity, high specific capacity and excellent environmental stability. However, the research data show that the cycle life of the polyaniline capacitor hardly exceeds 10000 times, and the specific capacitance value is reduced seriously during the cycle. This is because the doping/dedoping characteristics of polyaniline cause its volume to expand and contract repeatedly during charge and discharge, resulting in mechanical destruction of the electrode material during cycling. In addition, polyaniline is susceptible to oxidative degradation, which, even if slightly overcharged, would result in poor performance.
Currently, the preparation of polyaniline-based composite electrode materials is the main approach to improve cycle life, but also faces more serious challenges: polyaniline can effectively prolong the cycle life only by mixing with specific inorganic materials, such as carbon materials (activated carbon, carbon nano tubes, graphene and the like) or metal oxides (ruthenium oxide, nickel oxide, cobaltosic oxide and the like), the composite components are expensive, and the polyaniline can be uniformly mixed only by pretreatment and a special process, so that the preparation process is complex, time and labor are wasted, the cost is high, and some metal oxides have toxicity and do not meet the current requirements of green chemistry. Nevertheless, this technical approach still has difficulty dealing with the problem of oxidative degradation of polyaniline itself. In fact, polyaniline can be made more stable by chemical modification to form poly-N-methylaniline (PNMA) with higher oxidation resistance and better electrochemical activity. The poly-N-methylaniline being NH2One proton in the group is substituted with a methyl group, which stabilizes the positive charge generated by the nitrogen during oxidation, thereby increasing the stability of the polymer against electrochemical degradation.
The poly-N-methylaniline (PNMA) is very simple to prepare and can be obtained only by chemical oxidative polymerization or electrochemical polymerization of N-methylaniline monomers, but related documents of the polymer as an energy storage electrode material, particularly a supercapacitor material, report a few. The main reasons are that: (1) the substitution of methyl distorts the molecular chain of the polymer, destroys the conjugation property, leads to the reduction of the electrical property and has the conductivity of only 10-4～10-2S/cm which is far lower than 0.1-5S/cm of polyaniline; (2) PNMA (poly-n-vinyl-methacrylate) always forms smooth-surface microspheres spontaneously in the preparation process, and is difficult to form a porous nano structure with a larger specific surface area, and the porous nano structure is a key factor for improving the capacitance. It is seen that PNMA is difficult to be used as a mainstream energy storage electrode material in a super capacitor due to its own electrical properties and microstructure.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel. According to the preparation method, N-methylaniline is polymerized into poly-N-methylaniline (PNMA) under the initiation action of an oxidant, active groups such as hydroxyl, carbonyl, carboxylate ions, sulfonate ions and the like are rich in molecules of sodium alginate and lignosulfonate, and the sodium alginate, lignosulfonate and PNMA generate supermolecule self-assembly behavior by virtue of the hydrogen bond action of the active groups and PNMA molecular chains to form the dendritic polymer nano short fiber. Meanwhile, under the physical crosslinking action of the acidic doping agent, the dendritic polymer nano short fibers are mutually stacked and crosslinked to form a three-dimensional hierarchical porous structure with a nanoscale, so that the poly-N-methylaniline can be applied to the field of energy storage materials.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel comprises the following steps:
dissolving sodium alginate in deionized water, adding an acidic doping agent and N-methylaniline, performing ultrasonic treatment and stirring to dissolve uniformly to obtain a solution A;
dissolving an oxidant and lignosulfonate in deionized water, and uniformly stirring to obtain a solution B;
step three, respectively cooling the solution A obtained in the step one and the solution B obtained in the step two to 4 ℃, rapidly mixing and uniformly stirring, then placing the mixed solution at 0-4 ℃ for standing reaction, polymerizing the N-methylaniline into PNMA under the initiation action of an oxidant, because the molecules of sodium alginate and lignosulfonate are rich in active groups such as hydroxyl, carbonyl, carboxylate ions, sulfonate ions and the like, the sodium alginate, lignosulfonate and PNMA generate supermolecule self-assembly behavior and gradually gelate under the physical crosslinking action of an acidic doping agent by virtue of the hydrogen bond action of the active groups and PNMA molecular chains, and finally a PNMA/lignosulfonate hybrid hydrogel crude product is formed, the PNMA/lignosulfonic acid hybrid hydrogel crude product contains a small amount of unreacted N-methylaniline, an oxidant, sodium ions and other impurities;
and step four, placing the obtained crude PNMA/lignosulfonic acid hybrid hydrogel product in deionized water for purification and balance, removing impurities such as unreacted N-methylaniline monomer, oxidant, sodium ions and the like in the purification and balance process, and finally filtering to obtain the purified PNMA/lignosulfonic acid hybrid hydrogel.
The preparation method of the PNMA/lignosulfonic acid hybrid hydrogel with the hierarchical porous structure is characterized in that in the first step, the mass concentration of sodium alginate in the solution A is 0.1% -1%, the concentration of N-methylaniline is 0.5-2.5 mol/L, and the molar ratio of the acidic doping agent to the N-methylaniline is 0.2-0.5.
The preparation method of the PNMA/lignosulfonic acid hybrid hydrogel with the hierarchical porous structure is characterized in that in the first step, the acidic dopant is one or two of phytic acid, citric acid and tartaric acid.
The preparation method of the PNMA/lignosulfonic acid hybrid hydrogel with the hierarchical porous structure is characterized in that the molar ratio of the oxidant in the second step to the N-methylaniline in the first step is 0.25-1.5, and the mass of the lignosulfonate is 5% -15% of the mass of the N-methylaniline in the first step.
The preparation method of the PNMA/lignosulfonic acid hybrid hydrogel with the hierarchical porous structure is characterized in that in the second step, the oxidant is one or two of ammonium persulfate, potassium persulfate, ferric chloride and potassium permanganate.
The preparation method of the PNMA/lignosulfonic acid hybrid hydrogel with the hierarchical porous structure is characterized in that in the second step, the lignosulfonate is one or two of sodium lignosulfonate, magnesium lignosulfonate and calcium lignosulfonate.
The preparation method of the hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel is characterized in that the standing reaction time in the third step is 4-10 h.
The preparation method of the PNMA/lignosulfonic acid hybrid hydrogel with the hierarchical porous structure is characterized in that the evolution and equilibrium time in the fourth step is 48 hours, deionized water is replaced every 12 hours, and the volume of the deionized water is 25 times of the sum of the volumes of the solution A in the first step and the solution B in the second step.
Compared with the prior art, the invention has the following beneficial effects:
1. sodium alginate and lignin are natural polymers rich in reserves in nature, lignosulfonate is a derivative of lignin and a byproduct of the paper industry, and the lignosulfonate has high yield, low price and environmental friendliness and can endow materials with renewability. Therefore, the preparation method disclosed by the invention is simple and feasible, mild in reaction conditions, simple and convenient in post-treatment, low in equipment performance requirement, low in cost and environment-friendly.
2. In the preparation method, N-methylaniline is initiated by an oxidant to polymerize to generate PNMA, and sodium alginate and lignosulfonate molecules are rich in active groups such as hydroxyl, carbonyl, carboxylate ions, sulfonate ions and the like, so that the sodium alginate, lignosulfonate and PNMA generate supermolecule self-assembly behavior by virtue of the hydrogen bond action of the active groups and PNMA molecular chains to form the dendritic polymer nano short fibers. Meanwhile, under the physical crosslinking action of the acidic dopant, the dendritic polymer nano short fibers are mutually stacked and crosslinked to form a three-dimensional hierarchical porous structure with a nano scale, so that the problem of self microstructure limitation in the PNMA preparation process is solved. In addition, the lignosulfonate also has a doping effect on the PNMA, can promote electron movement, improves the crystallinity, enables the electrical property of the PNMA to be better, can further improve the electrochemical activity and the cycle stability, and solves the problem of poor electrical property of the PNMA to a certain extent.
3. The preparation method can obtain the nano-scale hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel. The material integrates the structure and performance advantages of PNMA and hydrogel, overcomes the defects of PNMA, shows higher specific capacitance and cycle life, has specific capacitance value of 350-420F/g, is obviously higher than polyaniline (about 200F/g) prepared by the traditional chemical oxidation method, even higher than polyaniline composite electrode materials reported in some documents, and is particularly suitable for energy storage electrode materials. In addition, based on the nano-scale hierarchical porous structure and good hydrophilicity, the material has wide application prospects in the fields of sensing, catalysis, heavy metal ion adsorption and the like.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a scanning electron microscope image of PNMA/lignosulfonic acid hybrid hydrogel prepared in example 1 of the present invention after freeze-drying.
FIG. 2 is a constant current charge and discharge curve of PNMA/lignosulfonic acid hybrid hydrogel prepared in example 1 of the present invention.
FIG. 3 is a cycling stability curve for 12000 cycles of the PNMA/lignosulfonic acid hybrid hydrogel prepared in example 1 of this invention.
Detailed Description
Example 1
The preparation method of this example includes the following steps:
step one, dissolving 0.05g of sodium alginate in 10mL of deionized water, adding 3.3g of phytic acid and 2.68g N-methylaniline, and carrying out ultrasonic treatment and stirring to uniformly dissolve the phytic acid and the 2.68g N-methylaniline to obtain a solution A;
step two, dissolving 2.85g of ammonium persulfate and 0.268g of sodium lignosulfonate in 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, respectively cooling the solution A obtained in the step one and the solution B obtained in the step two to 4 ℃, rapidly mixing and uniformly stirring, then placing the mixed solution at 2 ℃ for standing reaction for 8 hours, and obtaining a PNMA/lignosulfonic acid hybrid hydrogel crude product after the reaction is finished, wherein the PNMA/lignosulfonic acid hybrid hydrogel crude product contains impurities such as N-methylaniline, oxidant, sodium ions and the like which do not participate in the polymerization reaction;
step four, placing the crude PNMA/lignosulfonic acid hybrid hydrogel obtained in the step three in deionized water, purifying and balancing for 48 hours, wherein the deionized water is replaced every 12 hours, the volume of the deionized water used in the purification and balancing is 25 times of the sum of the volumes of the solution A in the step one and the solution B in the step two, unreacted N-methylaniline monomer, oxidant, sodium ions and other impurities can be removed, and finally, pure PNMA/lignosulfonic acid hybrid hydrogel is obtained through filtration.
FIG. 1 is a scanning electron micrograph of the PNMA/lignosulfonic acid hybrid hydrogel prepared in this example, after freeze-drying. The figure shows a hierarchical porous structure of stacked cross-linked dendritic polymer nanofibrils (diameter <100nm) with both nanopores with a diameter less than 100nm and sub-nanopores with a diameter of hundreds of nanometers. The structure can effectively increase the electrochemical active surface of the material, is beneficial to obtaining higher specific capacitance and cycling stability, and solves the problems that a smooth-surface microsphere is always formed spontaneously in the preparation process of PNMA, a porous nano structure with larger specific surface area is difficult to form, and the PNMA is difficult to be used in the field of energy storage materials.
The reaction mechanism of this example is: n-methylaniline monomer is oxidized by ammonium persulfate to initiate polymerization to generate PNMA, and sodium alginate and sodium lignosulfonate molecules are rich in active groups such as hydroxyl, carbonyl, carboxylate ions, sulfonate ions and the like, so the sodium alginate, the sodium lignosulfonate and the PNMA can generate supermolecule self-assembly behavior by virtue of the hydrogen bond action of the active groups and PNMA molecular chains to form dendritic polymer nano short fibers. Meanwhile, under the physical crosslinking action of phytic acid, the dendritic polymer nano short fibers are mutually stacked and crosslinked to form a three-dimensional hierarchical porous structure with a nano scale (as shown in figure 1), and macroscopically, the reaction system is gelatinized to form the PNMA/lignosulfonic acid hybrid hydrogel material.
FIG. 2 is a constant current charge and discharge curve of the PNMA/lignosulfonic acid hybrid hydrogel prepared in this example. From the figure, the specific capacitance of the PNMA/lignosulfonic acid hybrid hydrogel prepared in the example at 0.5A/g is 418F/g, and the energy density is 28.4 Wh/kg.
FIG. 3 shows the cycling stability of PNMA/lignosulfonic acid hybrid hydrogel prepared in this example over 12000 cycles. As can be seen from FIG. 3, after 12000 cycles, the specific capacitance of the PNMA/lignosulfonic acid hybrid hydrogel is reduced by about 32%, while the specific capacitance of the polyaniline electrode material prepared by the traditional method is reduced by more than 60% after 8000 cycles, and the cycle life is difficult to exceed 10000. Therefore, the PNMA/lignosulfonic acid hybrid hydrogel prepared by the method has a long cycle life.
Example 2
The preparation method of this example includes the following steps:
step one, dissolving 0.1g of sodium alginate in 10mL of deionized water, adding 0.450g of tartaric acid and 1.072g of N-methylaniline, and carrying out ultrasonic treatment and stirring to uniformly dissolve the sodium alginate and the N-methylaniline to obtain a solution A;
step two, dissolving 0.395g of potassium permanganate and 0.161g of magnesium lignosulfonate in 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, respectively cooling the solution A obtained in the step one and the solution B obtained in the step two to 4 ℃, then quickly mixing and uniformly stirring, then standing and reacting for 10 hours at 0 ℃, and obtaining a PNMA/lignosulfonic acid hybrid hydrogel crude product after the reaction is finished;
and step four, placing the crude PNMA/lignosulfonic acid hybrid hydrogel obtained in the step three in deionized water, purifying and balancing for 48 hours, wherein the deionized water is replaced every 12 hours, the volume of the deionized water used in purification and balancing is 25 times of the sum of the volumes of the solution A in the step one and the solution B in the step two, and finally filtering to obtain the pure PNMA/lignosulfonic acid hybrid hydrogel.
The specific capacitance and energy density of the PNMA/lignosulfonic acid hybrid hydrogel prepared in the example are 370F/g and 25.2Wh/kg respectively under the condition of 0.5A/g, and the specific capacitance is reduced by about 35% after 12000 times of circulation.
Example 3
The preparation method of this example includes the following steps:
step one, dissolving 0.3g of sodium alginate in 10mL of deionized water, adding 5.280g of phytic acid and 2.143g N-methylaniline, performing ultrasonic treatment and stirring to dissolve uniformly to obtain a solution A;
step two, 8.110g of potassium persulfate and 0.257g of sodium lignosulfonate are dissolved in 10mL of deionized water and stirred uniformly to obtain a solution B;
step three, respectively cooling the solution A obtained in the step one and the solution B obtained in the step two to 4 ℃, rapidly mixing and uniformly stirring, then standing and reacting for 6 hours at 4 ℃, and obtaining a PNMA/lignosulfonic acid hybrid hydrogel crude product after the reaction is finished;
and step four, placing the crude PNMA/lignosulfonic acid hybrid hydrogel obtained in the step three in deionized water, purifying and balancing for 48 hours, wherein the deionized water is replaced every 12 hours, the volume of the deionized water used in purification and balancing is 25 times of the sum of the volumes of the solution A in the step one and the solution B in the step two, and finally filtering to obtain the pure PNMA/lignosulfonic acid hybrid hydrogel.
The specific capacitance and energy density of the PNMA/lignosulfonic acid hybrid hydrogel prepared in the example are 402F/g and 27.4Wh/kg respectively under the condition of 0.5A/g, and the specific capacitance is reduced by about 35% after 12000 times of circulation.
Example 4
The preparation method of this example includes the following steps:
step one, dissolving 0.01g of sodium alginate in 10mL of deionized water, adding 0.480g of citric acid and 0.536g of N-methylaniline, and carrying out ultrasonic treatment and stirring to uniformly dissolve the sodium alginate and the N-methylaniline to obtain a solution A;
step two, dissolving 0.406g of ferric chloride and 0.027g of calcium lignosulfonate in 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, respectively cooling the solution A obtained in the step one and the solution B obtained in the step two to 4 ℃, then quickly mixing and uniformly stirring, then standing and reacting for 4 hours at 0 ℃, and obtaining a PNMA/lignosulfonic acid hybrid hydrogel crude product after the reaction is finished;
and step four, placing the crude PNMA/lignosulfonic acid hybrid hydrogel obtained in the step three in deionized water, purifying and balancing for 48 hours, wherein the deionized water is replaced every 12 hours, the volume of the deionized water used in purification and balancing is 25 times of the sum of the volumes of the solution A in the step one and the solution B in the step two, and finally filtering to obtain the pure PNMA/lignosulfonic acid hybrid hydrogel.
The specific capacitance and energy density of the PNMA/lignosulfonic acid hybrid hydrogel prepared in the example are 365F/g and 24.8Wh/kg respectively under the condition of 0.5A/g, and the specific capacitance is reduced by about 34% after 12000 times of circulation.
Example 5
The preparation method of this example includes the following steps:
step one, dissolving 0.01g of sodium alginate in 10mL of deionized water, adding 4.95g of phytic acid and 2.68g N-methylaniline, and carrying out ultrasonic treatment and stirring to uniformly dissolve the phytic acid and the 2.68g N-methylaniline to obtain a solution A;
step two, dissolving 2.703g of potassium persulfate, 3.423g of ammonium persulfate and 0.322g of sodium lignosulfonate in 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, respectively cooling the solution A obtained in the step one and the solution B obtained in the step two to 4 ℃, then quickly mixing and uniformly stirring, then standing and reacting for 4 hours at 3 ℃, and obtaining a PNMA/lignosulfonic acid hybrid hydrogel crude product after the reaction is finished;
and step four, placing the crude PNMA/lignosulfonic acid hybrid hydrogel obtained in the step three in deionized water, purifying and balancing for 48 hours, wherein the deionized water is replaced every 12 hours, the volume of the deionized water used in purification and balancing is 25 times of the sum of the volumes of the solution A in the step one and the solution B in the step two, and finally filtering to obtain the pure PNMA/lignosulfonic acid hybrid hydrogel.
The specific capacitance and energy density of the PNMA/lignosulfonic acid hybrid hydrogel prepared in the example are 400F/g and 27.2Wh/kg respectively under the condition of 0.5A/g, and the specific capacitance is reduced by about 37% after 12000 times of circulation.
Example 6
The preparation method of this example includes the following steps:
step one, dissolving 0.08g of sodium alginate in 10mL of deionized water, adding 0.096g of citric acid, 1.32g of phytic acid and 1.072g N-methylaniline, and carrying out ultrasonic treatment and stirring to uniformly dissolve the sodium alginate, the phytic acid and the methylaniline to obtain a solution A;
step two, dissolving 0.811g of potassium persulfate, 0.324g of ferric chloride, 0.096g of sodium lignosulfonate and 0.065g of magnesium lignosulfonate in 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, respectively cooling the solution A obtained in the step one and the solution B obtained in the step two to 4 ℃, then quickly mixing and uniformly stirring, then standing and reacting for 6 hours at the temperature of 2 ℃, and obtaining a PNMA/lignosulfonic acid hybrid hydrogel crude product after the reaction is finished;
and step four, placing the crude PNMA/lignosulfonic acid hybrid hydrogel obtained in the step three in deionized water, purifying and balancing for 48 hours, wherein the deionized water is replaced every 12 hours, the volume of the deionized water used in purification and balancing is 25 times of the sum of the volumes of the solution A in the step one and the solution B in the step two, and finally filtering to obtain the pure PNMA/lignosulfonic acid hybrid hydrogel.
The specific capacitance and energy density of the PNMA/lignosulfonic acid hybrid hydrogel prepared in the example are 378F/g and 25.7Wh/kg respectively under the condition of 0.5A/g, and the specific capacitance is reduced by about 30% after 12000 times of circulation.
Example 7
The preparation method of this example includes the following steps:
step one, dissolving 0.08g of sodium alginate in 10mL of deionized water, adding 1.65g of phytic acid, 0.375g of tartaric acid and 1.072g N-methylaniline, and carrying out ultrasonic treatment and stirring to uniformly dissolve the sodium alginate and the phytic acid to obtain a solution A;
step two, dissolving 0.342g of ammonium persulfate, 0.162g of ferric chloride, 0.057g of sodium lignosulfonate and 0.05g of calcium lignosulfonate in 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, respectively cooling the solution A obtained in the step one and the solution B obtained in the step two to 4 ℃, then quickly mixing and uniformly stirring, then standing and reacting for 8 hours at 0 ℃, and obtaining a PNMA/lignosulfonic acid hybrid hydrogel crude product after the reaction is finished;
and step four, placing the crude PNMA/lignosulfonic acid hybrid hydrogel obtained in the step three in deionized water, purifying and balancing for 48 hours, wherein the deionized water is replaced every 12 hours, the volume of the deionized water used in purification and balancing is 25 times of the sum of the volumes of the solution A in the step one and the solution B in the step two, and finally filtering to obtain the pure PNMA/lignosulfonic acid hybrid hydrogel.
The specific capacitance and energy density of the PNMA/lignosulfonic acid hybrid hydrogel prepared in the example are 384F/g and 26.1Wh/kg respectively under the condition of 0.5A/g, and the specific capacitance is reduced by about 33% after 12000 times of circulation.
Example 8
The preparation method of this example includes the following steps:
step one, dissolving 0.1g of sodium alginate in 10mL of deionized water, adding 0.188g of tartaric acid, 0.240g of citric acid and 0.536g N-methylaniline, and carrying out ultrasonic treatment and stirring to uniformly dissolve the mixture to obtain a solution A;
step two, dissolving 0.608g of ferric chloride, 0.593g of potassium permanganate, 0.02g of magnesium lignosulfonate and 0.007g of calcium lignosulfonate in 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, respectively cooling the solution A obtained in the step one and the solution B obtained in the step two to 4 ℃, rapidly mixing and uniformly stirring, then standing and reacting for 10 hours at 4 ℃, and obtaining a PNMA/lignosulfonic acid hybrid hydrogel crude product after the reaction is finished;
and step four, placing the crude PNMA/lignosulfonic acid hybrid hydrogel obtained in the step three in deionized water, purifying and balancing for 48 hours, wherein the deionized water is replaced every 12 hours, the volume of the deionized water used in purification and balancing is 25 times of the sum of the volumes of the solution A in the step one and the solution B in the step two, and finally filtering to obtain the pure PNMA/lignosulfonic acid hybrid hydrogel.
The specific capacitance and energy density of the PNMA/lignosulfonic acid hybrid hydrogel prepared in the example are 391F/g and 26.6Wh/kg respectively under the condition of 0.5A/g, and the specific capacitance is reduced by about 36% after 12000 times of circulation.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalent changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (6)
1. A preparation method of hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel is characterized by comprising the following steps:
dissolving sodium alginate in deionized water, adding an acidic doping agent and N-methylaniline, performing ultrasonic treatment and stirring to dissolve uniformly to obtain a solution A;
dissolving an oxidant and lignosulfonate in deionized water, and uniformly stirring to obtain a solution B;
step three, respectively cooling the solution A obtained in the step one and the solution B obtained in the step two to 4 ℃, then quickly mixing and uniformly stirring, and then carrying out standing reaction at the temperature of 0-4 ℃ to obtain a PNMA/lignosulfonic acid hybrid hydrogel crude product;
step four, putting the crude PNMA/lignosulfonic acid hybrid hydrogel obtained in the step three into deionized water for purification and balance, and filtering after purification and balance to obtain purified PNMA/lignosulfonic acid hybrid hydrogel;
in the first step, the mass concentration of the sodium alginate in the solution A is 0.1-1%, the concentration of the N-methylaniline is 0.5-2.5 mol/L, and the molar ratio of the acidic doping agent to the N-methylaniline is 0.2-0.5; the molar ratio of the oxidant to the N-methylaniline in the step two is 0.25-1.5, and the mass of the lignosulfonate is 5% -15% of the mass of the N-methylaniline in the step one.
2. The preparation method of the hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel according to claim 1, characterized in that in step one, the acidic dopant is one or two of phytic acid, citric acid and tartaric acid.
3. The preparation method of the hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel according to claim 1, wherein in step two the oxidizing agent is one or two of ammonium persulfate, potassium persulfate, ferric chloride, and potassium permanganate.
4. The preparation method of the hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel according to claim 1, wherein in step two the lignosulfonate is one or two of sodium lignosulfonate, magnesium lignosulfonate and calcium lignosulfonate.
5. The preparation method of the hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel according to claim 1, characterized in that the standing reaction time in step three is 4-10 h.
6. The method for preparing hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel according to claim 1, characterized in that the time for purification equilibrium in step four is 48h, wherein deionized water is replaced every 12h, and the volume of deionized water used is 25 times the sum of the volumes of solution A in step one and solution B in step two.
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| CN105885065A (en) * | 2016-05-13 | 2016-08-24 | 西南交通大学 | Preparation method of electrical stimulation-near infrared dual response high strength hydrogel |
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