CN113444371A - Preparation method and application of metal organic framework/polyaniline composite material - Google Patents
Preparation method and application of metal organic framework/polyaniline composite material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a metal organic framework/polyaniline composite material. And synthesizing an unsaturated coordination metal organic framework material by changing the proportion of the organic ligand and the solvent through a hydrothermal method, taking the unsaturated coordination metal organic framework material as a doping agent of polyaniline, forming a composite material by doping and polyaniline, and applying the composite material to a water-system zinc ion battery anode material. Through the proton doping effect of the functional acid groups which are not coordinated in the unsaturated coordination metal organic framework on the polyaniline, the proton concentration of polyaniline self-doping is improved, the electrochemical activity of the polyaniline is further improved, and the constructed water system zinc ion secondary battery has higher specific capacity and good rate capability. The raw materials used in the invention are renewable and environment-friendly, and have good application prospect in the aspect of large-scale energy storage of the water system zinc ion battery.
Description
Technical Field
The invention relates to the field of water-based zinc ion batteries, in particular to a preparation method and application of a metal organic framework/polyaniline composite material.
Background
In recent years, a water-based zinc ion battery is a novel secondary electrochemical battery which is popular in recent years, and has high application value and development prospect in the field of large-scale energy storage due to the advantages of high energy density, high power density, nontoxic battery materials, low price, simple preparation process and the like. The water system zinc ion battery shows huge potential on large-scale energy storage due to lower oxidation-reduction potential (-0.76V), high theoretical specific capacity (820 mAh/g), good environmental stability, low cost and high safety, and is widely concerned by academia. Although Zn2+Ionic radius of (0.074 nm) and Li+(0.076 nm) close to that of the above-mentioned metal oxide, but high in Zn content due to its high mass, large charge radius and large electrostatic repulsion2+The kinetics of intercalation are retarded. One of the difficulties in developing zinc ion batteries is finding a suitable positive electrode material to improve the performance of the zinc ion batteries.
The positive electrode material provides a storage site for zinc and largely determines the voltage and capacity of the zinc ion battery. The main challenges of the positive electrode material are the controversial reaction mechanism, rapid capacity fading, low specific capacity and poor rate capability. Among a plurality of anode materials, the organic material has the advantages of large theoretical capacity, flexible structural design, high element abundance, environmental friendliness, sustainability and the like, can obtain high working voltage through molecular structure and group regulation, and is an attractive electrode material. The conductive polymer polyaniline has the advantages of high oxidation-reduction potential, high conductivity, stable structure, easy processing into flexible electrodes and the like, and is widely applied to energy storage systems such as lithium/sodium ion batteries, super capacitors and the like, but the application in water system zinc ion anode materials is still in a budding state, and related researches at home and abroad are few. The main reason is that the electrolyte is mainly neutral or alkaline because the zinc cathode of the water-based zinc ion battery is easy to corrode and react with hydrogen in the acidic electrolyte. The polyaniline has higher conductivity and electrochemical activity only in an acidic environment (pH is less than or equal to 4) rich in protons, and the contradiction between the two causes limits the application of the conductive polymer in a water-based zinc ion battery. Therefore, how to improve the dependence of polyaniline electric activity on the pH of the electrolyte so as to improve the conductivity, the structural stability and the electrochemical activity of the neutral electrolyte becomes a key for solving the problems. The electrochemical stability and proton-rich doping/dedoping of polyaniline molecules are enhanced, a new way of establishing the proton autodoping capability, low molecular weight and high structural stability of the polyaniline molecules is established, and the method is an important scientific problem which is urgently needed to be solved in the field of large-scale energy storage of neutral water system zinc ion batteries.
The method disclosed by the Chinese patent application publication Nos. CN107887603A, CN111682179A, CN110061308A, CN110767911A, CN110660992A and the like adopts a hydrothermal method to prepare the metal organic framework or the positive electrode material compounded with polyaniline, and improves the electrochemical performance of the traditional organic micromolecule electrode by virtue of the porous and insoluble characteristics of the metal organic framework, but the gram capacity of the traditional organic micromolecule electrode is difficult to improve due to the large molecular weight and the few active groups.
The research on the influence of different metal organic frameworks on the performance of the zinc ion battery is researched by the promise of the Qinghua university, and the research shows that the carboxylic acid group in the organic ligand can participate in the storage of zinc ions; the J. Fraser Stoddart copper-based conductive metal organic framework of the northwest university of America is used as a zinc ion anode material, the multiplying power of the material is effectively improved, but the specific capacity and the cycling stability of the two materials are not effectively improved.
YIng Liu et al prepared blends of PEDOT, PSS and polyaniline, -SO3−H+The group serves as an internal proton reservoir and provides enough H + for the protonation of PANI, so that the electrochemical activity of the PANI is improved; hyunjin Yu et al, which adopts inorganic carbon fibers containing-OH, -COOH and polyaniline to form a compound, obtained a specific capacity of 112.84 mA h/g, and the capacity retention rate after 100 cycles is 86%. However, the simple physical compounding is adopted, the stability of the composite material is poor, and the cycle performance of the material is to be improved.
Disclosure of Invention
In view of the above, there is a need to provide a method for preparing a metal organic framework/polyaniline composite material with high specific capacity and excellent stability, and an application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows: a preparation method of a metal organic framework/polyaniline composite material comprises the following steps:
s1: ultrasonically dispersing an aniline monomer and a surfactant in a first solvent to obtain a uniform solution A;
s2: dissolving an oxidant and an acid in a second solvent to form solution B;
s3: stirring the solution B in an ice bath environment, slowly dripping the solution B into the solution A, and continuously reacting for a certain time to obtain a polyaniline mixed solution C;
s4: dispersing organic ligand in the polyaniline mixed solution C, dropwise adding a solution containing metal ion manganese, stirring at room temperature, transferring into a reaction kettle, reacting for a period of time, centrifuging, washing and drying to obtain the metal organic framework/polyaniline composite material.
Further, the surfactant is one or more of polyvinylpyrrolidone, betaine, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate or cetyl trimethyl ammonium bromide.
Further, the first solvent is one or more of deionized water, absolute ethyl alcohol, N-dimethylformamide, acetone or ethylene glycol polyethylene glycol; the second solvent is one or more of deionized water, N-dimethylformamide, acetone or polyethylene glycol.
Further, in step S2, the oxidant is one or more of ammonium persulfate, ferric chloride, hydrogen peroxide, or potassium permanganate; the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, tartaric acid, malic acid, citric acid or benzenesulfonic acid.
Further, in the step S3, the ice bath temperature of the solution B is-1-8 ℃; the stirring speed of the solution B in the ice bath environment is 200-300 r/min; the dropping speed of the solution A dropped into the solution B is 30-100 drops/min; the reaction time is 100-400 min.
Further, in step S4, the organic ligand is one or more of 2, 5-dihydroxyterephthalic acid, salicylic acid, sulfobenzoic acid, or pyromellitic acid; the solution of the metal ion manganese is one or more of manganese acetate, manganese sulfate, manganese chloride or manganese nitrate.
Further, the molar ratio of the organic ligand to manganese ions in the solution of metal ions manganese is 0.5-2: 1.
Further, in the step S4, performing a hydrothermal reaction in the reaction kettle, wherein the hydrothermal reaction temperature is 100-180 ℃, and the hydrothermal reaction time is 8-24 hours; the solvent for washing is one or more of deionized water, absolute ethyl alcohol, acetone or N, N-dimethylformamide.
In order to solve the technical problems, the second technical scheme of the invention is as follows: the material of the zinc ion battery anode comprises the metal organic framework/polyaniline composite material prepared by the preparation method.
The metal organic framework/polyaniline composite material used for the anode of the zinc ion battery skillfully self-assembles polyaniline and metal organic framework molecules into a composite by virtue of the positive and negative charge attraction and doping action between the functional groups which are not coordinated in the organic ligand and the polyaniline. By means of intermolecular force and the stability of the coordination covalent bond, the structural stability of the composite material is improved; the functional acid functional group which is not coordinated in the metal organic framework is utilized to provide abundant confined protons for the insertion/extraction of the protons of the polyaniline, so that the problem of low electrochemical activity of the polyaniline in neutral electrolyte due to the lack of protons is effectively solved; by means of the strong zinc storage performance, structural stability and porosity of the metal organic framework material and the high conductivity of polyaniline, the synergistic effect of 1+1 > 2 can be generated by compounding the metal organic framework material and the polyaniline, so that the high specific capacity and the excellent stability can be obtained.
In order to solve the technical problems, the third technical scheme of the invention is as follows: a zinc ion battery comprises a zinc ion battery body, wherein the positive electrode of the zinc ion battery body adopts the positive electrode of the zinc ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the raw materials adopted by the method are renewable, all are organic matters, and the synthesis method is simple and controllable.
2. The metal organic framework has a unique structure, and the confined protonation of polyaniline is realized by using the protonic acid group in the metal organic framework, so that the electrochemical activity of the polyaniline is improved.
3. By means of the renewable raw materials, the structural stability and the zinc storage activity of the metal organic framework, a reference thought is provided for the modification of polyaniline and the design and preparation of novel organic electrodes.
In order to make the aforementioned and other objects, features and advantages of the invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is an SEM image of a product prepared according to one embodiment of the invention.
Figure 2 shows the pseudocapacitance contribution rate of a button cell assembled by the product prepared by the invention.
Fig. 3 is a multiplying power diagram of a button cell assembled by the product prepared by the invention and tested.
Fig. 4 is a graph of the cycling performance of the test in which the product prepared by the invention is assembled into a button cell.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments.
Example one
A preparation method of a metal organic framework/polyaniline composite material comprises the following steps:
s1: adding 1.5 mL of aniline monomer into a first solvent consisting of 30 mL of deionized water/N, N-dimethylformamide, adding 0.5 g of N-methylpyrrolidone, and performing ultrasonic dispersion for 5min to obtain a solution A and transferring the solution A into a constant-pressure titration funnel;
s2: dissolving a certain amount of ammonium persulfate (the molar ratio of the ammonium persulfate to the aniline monomer is 1.2: 1) in deionized water (namely a second solvent), adjusting the pH of the solution to 1-3 by using hydrochloric acid, and performing ultrasonic dispersion for 5min to form solution B;
s3: transferring the solution B into a three-neck flask, placing the three-neck flask into an ice bath environment (the ice bath temperature is 0 ℃) and stirring (the stirring speed is 250 r/min), meanwhile, dripping the solution A into the three-neck flask at the speed of 40-60 drops per minute, and reacting for 6 hours in ice bath to obtain polyaniline mixed solution C;
s4: adding 40 mmol of manganese acetate and 20 mmol of 2, 5-dihydroxy terephthalic acid into the polyaniline mixed solution C, and continuously stirring and reacting for 5 hours at room temperature;
s5: then transferring the solution obtained in the step S4 into a reaction kettle, and carrying out hydrothermal reaction at 140 ℃ for 20 h;
s6: and cooling to room temperature, washing with deionized water and absolute ethyl alcohol, and drying at 70 ℃ to obtain the metal organic framework/polyaniline composite material.
An SEM image of the metal organic framework/polyaniline composite material obtained by the above preparation method is shown in fig. 1.
Example two
A preparation method of a metal organic framework/polyaniline composite material comprises the following steps:
s1: 40 mmol of manganese acetate is dissolved in 20 mL of deionized water and transferred to a three-neck flask;
s2: dissolving 20 mmol of 2, 5-dihydroxy terephthalic acid in 1M sodium hydroxide solution, dripping into a three-neck flask under stirring, and reacting at room temperature for 5 h;
s3: adding 1.5 mL of aniline monomer into 30 mL of deionized water/N, N-dimethylformamide solution, adding 0.5 g of N-methylpyrrolidone, ultrasonically dispersing for 5min, and transferring into a three-neck flask;
s4: dissolving a certain amount of ammonium persulfate (the molar ratio of the ammonium persulfate to the aniline monomer is 1.2: 1) in deionized water, adjusting the dissolved pH to 1-3 by using hydrochloric acid, ultrasonically dispersing for 5min, transferring into a constant-pressure titration funnel, dripping into a three-neck flask under stirring at the speed of 40-60 drops per minute, and reacting in an ice bath for 8 h to form a mixed solution;
s5: then transferring the S4 solution into a reaction kettle, and carrying out hydrothermal reaction at 140 ℃ for 20 h;
s6: and cooling to room temperature, washing with deionized water and absolute ethyl alcohol, and drying at 70 ℃ overnight to obtain the metal organic framework/polyaniline composite material.
The preparation method and the method adopted in the first embodiment have different adding sequences, and the same product can be obtained.
EXAMPLE III
Zinc ion battery anode
At normal temperature and pressure, 0.02g of conductive carbon black was added to 1g of a 2wt% N-methylpyrrolidone solution of polyvinylidene fluoride to obtain a mixed solution. After stirring for 30min, 0.16g of the metal organic framework/polyaniline composite material (active material, conductive carbon black, PVDF mass ratio is 8:1: 1) prepared in the first example is added to the mixed solution, and the mixture is stirred for 6 hours to obtain a uniformly mixed positive electrode slurry. The obtained slurry was uniformly coated on the surface of a titanium foil 10um thick. And drying the coated titanium foil at 80 ℃, and cutting into small wafers with the diameter of 15mm to obtain the zinc ion battery anode.
A 2032 type button cell using the positive electrode of the zinc ion battery.
The zinc foil with the thickness of 0.1mm is cut into small 15mm pieces as the negative electrode material of the battery, the glass fiber filter paper with the thickness of 16mm is used as the positive and negative electrode separation membrane, and the zinc trifluoromethanesulfonate aqueous solution with the thickness of 2M is used as the electrolyte to assemble the CR2032 type button zinc ion battery.
And (3) testing the pseudocapacitance property of the assembled zinc ion battery.
The pseudocapacitance properties of the prepared zinc ion cells were tested at room temperature using the electrochemical workstation CHI 760E. The obtained zinc ion battery was clamped into a CHI760E electrochemical workstation, and CV curves of the zinc ion battery were measured at different scan rates and voltage windows of 1.9-1V by cyclic voltammetry. And simulating the occupation ratio of the pseudocapacitance in the total capacity of the zinc ion battery according to the obtained CV curve. The different scan rates were 0.1, 0.3, 0.5, 0.7, 1.0mV/s, respectively.
As can be seen from fig. 2, the contribution ratios of the pseudocapacitance characteristics in the total specific capacity of the zinc ion battery are 64%, 69%, 73%, 81% and 92% in this order. The zinc ion battery taking the metal organic framework/polyaniline composite material as the anode material has good rate capability.
And testing the battery rate performance of the assembled zinc ion battery.
And (3) testing the rate capability of the prepared zinc ion battery at room temperature by using a Newware battery testing system. The prepared zinc ion battery is clamped into a Newware battery tester, and the current density is set to be 100, 200, 500, 1000 and 3000 mA/g in sequence, so that the rate performance map of the prepared zinc ion battery is obtained.
As shown in fig. 3, the results show that the metal organic framework/polyaniline composite material prepared in the invention exhibits more excellent rate performance as the positive electrode material of the zinc ion battery. This is largely attributed to the enhanced electrochemical activity of polyaniline due to its special confined protonation structure.
And testing the charge-discharge long cycle performance of the assembled zinc ion battery.
And (3) testing the long-cycle performance of the prepared zinc ion battery at room temperature by using a newware battery testing system. And clamping the obtained zinc ion battery on a neware battery tester, setting the current density to be 100 mA/g, and circulating for 100 circles to obtain a charge-discharge long-circulation performance map of the obtained zinc ion battery.
As shown in FIG. 4, the result shows that the metal organic framework/polyaniline composite material prepared by the method has better stability as the zinc battery anode material.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a metal organic framework/polyaniline composite material is characterized by comprising the following steps:
s1: ultrasonically dispersing an aniline monomer and a surfactant in a first solvent to obtain a uniform solution A;
s2: dissolving an oxidant and an acid in a second solvent to form solution B;
s3: stirring the solution B in an ice bath environment, slowly dripping the solution B into the solution A, and continuously reacting for a certain time to obtain a polyaniline mixed solution C;
s4: dispersing organic ligand in the polyaniline mixed solution C, dropwise adding a solution containing metal ion manganese, stirring at room temperature, transferring into a reaction kettle, reacting for a period of time, centrifuging, washing and drying to obtain the metal organic framework/polyaniline composite material.
2. The method for preparing a metal organic framework/polyaniline composite material as described in claim 1, wherein: the surfactant is one or more of polyvinylpyrrolidone, betaine, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate or cetyl trimethyl ammonium bromide.
3. The method for preparing a metal organic framework/polyaniline composite material as described in claim 1, wherein: the first solvent is one or more of deionized water, absolute ethyl alcohol, N-dimethylformamide, acetone or ethylene glycol polyethylene glycol; the second solvent is one or more of deionized water, N-dimethylformamide, acetone or polyethylene glycol.
4. The method for preparing a metal organic framework/polyaniline composite material as described in claim 1, wherein: in step S2, the oxidant is one or more of ammonium persulfate, ferric chloride, hydrogen peroxide or potassium permanganate; the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, tartaric acid, malic acid, citric acid or benzenesulfonic acid.
5. The method for preparing a metal organic framework/polyaniline composite material as described in claim 1, wherein: in the step S3, the ice bath temperature of the solution B is-1-8 ℃; the stirring speed of the solution B in the ice bath environment is 200-300 r/min; the dropping speed of the solution A dropped into the solution B is 30-100 drops/min; the reaction time is 100-400 min.
6. The method for preparing a metal organic framework/polyaniline composite material as described in claim 1, wherein: in step S4, the organic ligand is one or more of 2, 5-dihydroxyterephthalic acid, salicylic acid, sulfobenzoic acid, or pyromellitic acid; the solution of the metal ion manganese is one or more of manganese acetate, manganese sulfate, manganese chloride or manganese nitrate.
7. The method for preparing a metal organic framework/polyaniline composite material as described in claim 1, wherein: the molar ratio of the organic ligand to the manganese ions in the solution of the metal ions manganese is 0.5-2: 1.
8. The method for preparing a metal organic framework/polyaniline composite material as described in claim 1, wherein: in the step S4, carrying out hydrothermal reaction in a reaction kettle, wherein the hydrothermal reaction temperature is 100-180 ℃, and the hydrothermal reaction time is 8-24 h; the solvent for washing is one or more of deionized water, absolute ethyl alcohol, acetone or N, N-dimethylformamide.
9. A zinc ion battery positive electrode is characterized in that: the material of the positive electrode of the zinc ion battery comprises the metal organic framework/polyaniline composite material prepared by the preparation method of any one of claims 1 to 8.
10. A zinc ion battery comprises a zinc ion battery body and is characterized in that: the positive electrode of the zinc-ion battery body is the positive electrode of the zinc-ion battery according to claim 9.
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| CN115895279B (en) * | 2022-11-24 | 2023-07-21 | 西北大学 | SPAN/MOFs@Luminol luminescent material and preparation method and application thereof |
| CN117903341A (en) * | 2024-03-19 | 2024-04-19 | 辽宁鲁华泓锦新材料科技有限公司 | Method for removing catalyst metal component in cycloolefin-ethylene copolymer |
| CN117903341B (en) * | 2024-03-19 | 2024-05-28 | 辽宁鲁华泓锦新材料科技有限公司 | Method for removing catalyst metal component in cycloolefin-ethylene copolymer |
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