CN115873241A - Pyrene-dihydrophenazine-based conjugated microporous polymer, preparation method thereof and application of pyrene-dihydrophenazine-based conjugated microporous polymer as positive electrode active material of aluminum battery - Google Patents
Pyrene-dihydrophenazine-based conjugated microporous polymer, preparation method thereof and application of pyrene-dihydrophenazine-based conjugated microporous polymer as positive electrode active material of aluminum battery Download PDFInfo
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- CN115873241A CN115873241A CN202111147820.XA CN202111147820A CN115873241A CN 115873241 A CN115873241 A CN 115873241A CN 202111147820 A CN202111147820 A CN 202111147820A CN 115873241 A CN115873241 A CN 115873241A
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- dihydrophenazine
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000007774 positive electrode material Substances 0.000 title description 11
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000006183 anode active material Substances 0.000 claims abstract description 7
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- -1 (2 ' -amino- [1,1' -biphenyl ] -2-yl) (dicyclohexyl (2 ',6' -diisopropoxy- [1,1' -biphenyl ] -2-yl) phosphoryl) palladium chloride Chemical compound 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
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- 229940078552 o-xylene Drugs 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
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- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 claims 1
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- 125000003118 aryl group Chemical group 0.000 description 3
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- ZIZMDHZLHJBNSQ-UHFFFAOYSA-N 1,2-dihydrophenazine Chemical group C1=CC=C2N=C(C=CCC3)C3=NC2=C1 ZIZMDHZLHJBNSQ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- 229910000838 Al alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 239000011149 active material Substances 0.000 description 1
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- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a pyrene-dihydrophenazine conjugated microporous polymer, a preparation method thereof and application of the pyrene-dihydrophenazine conjugated microporous polymer as an aluminum battery anode active material, wherein the polymer is a highly cross-linked conjugated microporous polymer prepared from 1,3,6,8-tetrabromopyrene and 5,10-dihydrophenazine through a simple Buchwald-Hartwig coupling reaction, has the characteristics of a conjugated structure and a porous material cross-linking porosity of a traditional conjugated polymer, solves the problem of dissolution of an organic micromolecule or linear polymer electrode material in an ionic electrolyte when being used as the aluminum battery anode active material, has the advantages of high specific capacity, good rate performance, long cycle life and the like, is simple in preparation process, low in price and easy to obtain raw materials, and is expected to become a next-generation green, environment-friendly, sustainable and high-performance aluminum battery electrode material.
Description
Technical Field
The invention belongs to the technical field of organic battery materials, and particularly relates to a pyrene-dihydrophenazinyl conjugated microporous polymer for an aluminum battery positive electrode active material and a preparation method of the polymer.
Background
In recent years, electrochemical energy storage technology is receiving attention, but the traditional lithium ion battery faces the problems of resource shortage, poor safety and the like. Aluminum element is abundant in earth crust, the problem of resource shortage is solved, a non-flammable and electrochemically stable ionic electrolyte is used, the problem of safety is solved, and the redox reaction of three electrons enables aluminum metal to have extremely high energy density as a battery cathode, so that the aluminum battery is considered to be an extremely competitive secondary battery technology. However, the positive electrode material has a decisive influence on the performance of the aluminum battery. At present, inorganic positive electrode materials such as graphite and metal-based compounds are widely studied, but have problems of low specific capacity, low coulombic efficiency, high self-discharge, high degree of polarization, poor rate performance, short cycle life, and the like. Compared with inorganic materials, the organic electrode has the advantages of abundant resources, environmental friendliness, reproducibility, easy structure regulation and control and the like. Organic small molecule or linear polymer electrode materials are reported to have different dissolution problems in an ionic electrolyte, so that the cycling stability is poor. In addition, the linear polymer macromolecular chains are in a close-packed structure, which not only hinders effective contact between active sites in the electrode material and electrolyte, but also hinders transmission of charge carriers, thereby resulting in low specific capacity and poor rate performance. The conjugated microporous polymer has the characteristics of conjugated structure and porous material crosslinking porosity of the traditional conjugated polymer, and provides a plurality of advantages for the conjugated microporous polymer to be used as an anode active material of an aluminum battery. The conjugated structure of the conjugated microporous polymer promotes the transmission of current carriers along a macromolecular chain, and is favorable for realizing high electrochemical activity and excellent dynamic performance; the highly crosslinked molecular structure of the conjugated microporous polymer can effectively inhibit the conjugated microporous polymer from dissolving in the ionic electrolyte, and is favorable for realizing long cycle life; the rich pore structure and the high specific surface area of the conjugated microporous polymer provide a channel for the transmission of charge carriers, promote the contact of electrolyte and active sites, and are favorable for realizing high electrochemical activity and excellent dynamic performance; the abundance of monomer types and the diversity of synthetic methods allow the structural composition of the conjugated microporous polymers to be fine-tuned by varying the reaction conditions and the structure of the monomers. Based on the unique structural advantages, the design and development of the conjugated microporous polymer cathode material are expected to realize a new breakthrough of the comprehensive performance of the aluminum battery.
Disclosure of Invention
The invention aims to provide a pyrene-dihydrophenazine conjugated microporous polymer which is used for an aluminum battery positive electrode active material and has high specific capacity, good rate performance and long cycle life, and provides a preparation method which has simple steps and high yield for the polymer.
Aiming at the purposes, the structure of the pyrene-dihydrophenazine-based conjugated microporous polymer adopted by the invention is as follows:
the preparation method of the pyrene-dihydrophenazine conjugated microporous polymer comprises the following steps: under the protection of nitrogen, adding 5,10-dihydrophenazine, 1,3,6,8-tetrabromophyrene, a ligand, a palladium catalyst and sodium tert-butoxide into a Schlenk tube, adding an organic solvent, heating to reflux and reacting for 24-72 hours, cooling to room temperature after the reaction is finished, washing with dichloromethane, methanol and water, refluxing with tetrahydrofuran, extracting in a Soxhlet extractor, and drying in vacuum to obtain the pyrene-dihydrophenazine conjugated microporous polymer, wherein the reaction equation is as follows:
in the above preparation method, it is preferable that the molar ratio of 5,10-dihydrophenazine to 1,3,6,8-tetrabromophene is 1.
In the preparation method, the ligand is preferably any one of 2-dicyclohexylphosphine-2 ',6' -diisopropoxy-1,1 ' -biphenyl, 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl and tri-tert-butylphosphine; preferably, the palladium catalyst is any one of (2 ' -amino- [1,1' -biphenyl ] -2-yl) (dicyclohexyl (2 ',6' -diisopropyloxy- [1,1' -biphenyl ] -2-yl) phosphoryl) palladium chloride, bis (dibenzylideneacetone) and palladium acetate.
In the preparation method, the addition amount of the ligand is preferably 1 to 5 percent of the molar amount of 5,10-dihydrophenazine, the addition amount of the palladium catalyst is preferably 1 to 5 percent of the molar amount of 5,10-dihydrophenazine, and the addition amount of the sodium tert-butoxide is preferably 3 to 7 times of the molar amount of 5,10-dihydrophenazine.
In the above preparation method, the organic solvent is preferably any one of toluene, o-xylene, 1,4-dioxane and tetrahydrofuran.
The pyrene-dihydrophenazine conjugated microporous polymer can be used as an active material of the anode of an aluminum battery, and is assembled into the aluminum battery with metal aluminum or aluminum alloy as the cathode and aluminum chloride-based ionic liquid as electrolyte.
The invention has the following beneficial effects:
1. the pyrene-dihydrophenazine conjugated microporous polymer is prepared by adopting a simple Buchwald-Hartwig coupling reaction, the raw materials are cheap and easy to obtain, the preparation process is simple, and the cost of the battery is effectively reduced.
2. The pyrene-dihydrophenazine conjugated microporous polymer is rich in two redox active units of pyrene and dihydrophenazine, the utilization rate of active sites is high, and when the pyrene-dihydrophenazine conjugated microporous polymer is used as an aluminum battery anode active material, a conjugated macromolecular chain of the conjugated microporous polymer is oxidized to lose electrons in a charging process to form a positive ion free radical with positive charges; in the discharging process, positive charge cation free radicals generated on the macromolecular chain of the conjugated microporous polymer accept electrons and are reduced to an initial neutral state, and stored anions are released into the electrolyte, so that the specific capacity of the aluminum battery is effectively improved, and the aluminum battery with high specific capacity, good rate capability and long cycle life is finally obtained.
3. The pyrene-dihydrophenazine conjugated microporous polymer has a highly crosslinked molecular structure, and effectively solves the problem of dissolution of small molecules or linear polymers in an ionic electrolyte, so that the circulation stability of an aluminum battery is improved. Meanwhile, the abundant pore structure and the high specific surface area of the polymer provide channels for the transmission of charge carriers, and promote the contact of an ionic electrolyte and an active site, so that the aluminum battery is favorable for realizing high electrochemical activity and excellent dynamic performance. Compared with most reported organic anode materials, the aluminum battery taking the pyrene-dihydrophenazine conjugated microporous polymer as the anode active material shows excellent electrochemical performance, and is at the leading level at home and abroad.
Drawings
FIG. 1 is an infrared spectrum of a pyrene-dihydrophenazine based conjugated microporous polymer prepared in example 1.
FIG. 2 is a solid NMR carbon spectrum of a pyrene-dihydrophenazine based conjugated microporous polymer prepared in example 1.
FIG. 3 is an XRD spectrum of the pyrene-dihydrophenazine based conjugated microporous polymer prepared in example 1.
FIG. 4 is a graph of nitrogen adsorption-desorption curves for pyrene-dihydrophenazine based conjugated microporous polymer prepared in example 1.
FIG. 5 is a graph of the pore size distribution of the pyrene-dihydrophenazine based conjugated microporous polymer prepared in example 1.
FIG. 6 is a SEM photograph of a pyrene-dihydrophenazine based conjugated microporous polymer prepared in example 1.
FIG. 7 is a cyclic voltammogram of an aluminum battery prepared using the pyrene-dihydrophenazine based conjugated microporous polymer of example 1 as a positive electrode active material.
FIG. 8 is a constant current charge and discharge curve of an aluminum battery prepared using the pyrene-dihydrophenazine based conjugated microporous polymer of example 1 as a positive electrode active material.
Fig. 9 is a rate capability of an aluminum battery prepared using the pyrene-dihydrophenazine based conjugated microporous polymer of example 1 as a positive electrode active material.
FIG. 10 is a graph showing the cycle characteristics of an aluminum battery prepared using the pyrene-dihydrophenazine-based conjugated microporous polymer of example 1 as a positive electrode active material.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
Under nitrogen protection, 6mL of toluene was added to a Schlenk tube containing 182mg (1.00 mmol) of 5,10-dihydrophenazine, 257mg (0.50 mmol) of 1,3,6,8-tetrabromophyrene, 14mg (0.03 mmol) of 2-dicyclohexylphosphine-2 ',6' -diisopropoxy-1,1 '-biphenyl, 23mg (0.03 mmol) (2' -amino- [1,1 '-biphenyl ] -2-yl) (dicyclohexyl (2', 6 '-diisopropoxy- [1,1' -biphenyl ] -2-yl) phosphoryl) palladium chloride and 481mg (5.00 mmol) of sodium tert-butoxide, heated to 115 ℃ for reflux reaction for 48 hours, cooled to room temperature after the reaction is completed, washed with dichloromethane, methanol and water for a plurality of times, and extracted with tetrahydrofuran in a Soxhlet extractor, dried under vacuum at 100 ℃ for 24 hours to give a red solid powder, i.e., pyrene-dihydrophenazine conjugated microporous polymer.
The chemical structure of the obtained red solid powder is characterized by adopting an infrared spectrum and a solid nuclear magnetic carbon spectrum, and the result is shown in the figures 1-2. In FIG. 1, 1281cm -1 The peak at (A) is attributed to the vibration of the C-N bond, 1600cm -1 And 846cm -1 The peak at (A) is the vibration of the C = C bond on the aromatic ring of 1060cm -1 And 736cm -1 The peak at (A) is the out-of-plane vibration of the C-H bond on the aromatic ring. In FIG. 2, 114 to 138ppm are the peak-appearing signal regions at the carbon atoms of the aromatic ring, and 132ppm is the signal peak at the carbon atom bonded to the nitrogen atom of the dihydrophenazine unit. The XRD results of fig. 3 show that the obtained red solid powder is amorphous structure. The porosity of the red solid powder was characterized by a nitrogen adsorption-desorption curve, and the results are shown in fig. 4 to 5. As can be seen from FIG. 4, the specific surface area of the obtained red solid powder was 635m 2 g -1 . The pore size distribution results of fig. 5 indicate that the micropores of the resulting red solid powder are concentrated at 0.93nm, and the mesopores are mainly concentrated at 1.75nm. FIG. 6 is a scanning electron micrograph of a polymer showing a nanorod morphology.
Example 2
The application of the pyrene-dihydrophenazine-based conjugated microporous polymer prepared in the embodiment 1 as the positive electrode active material of the aluminum battery is specifically as follows:
mixing and grinding pyrene-dihydrophenazine-based conjugated microporous polymer, ketjen black and polyvinylidene fluoride according to the proportion of 1Uniformly dispersing to obtain uniformly mixed electrode slurry, coating the slurry on a tungsten mesh, and performing vacuum drying to obtain the pyrene-dihydrophenazine conjugated microporous polymer with the load of 1.70mg cm -2 And separating the anode and the cathode of the simple substance aluminum by using a diaphragm, injecting an aluminum chloride-chloridized-1-butyl-3-methylimidazole electrolyte with the molar ratio of 1.3, and assembling to obtain the aluminum battery taking the pyrene-dihydrophenazine-based conjugated microporous polymer as the anode active material. The assembled aluminum battery has the voltage range of 0-2V and the current density of 0.1-10A g at 25 DEG C -1 Constant current charge and discharge tests were performed and the results are shown in fig. 7-10. The cyclic voltammogram results of FIG. 7 show that the aluminum cell has distinct redox peaks at 0.45/0.33 and 1.46/1.40V. The constant current charge and discharge curve of FIG. 8 shows that the aluminum cell is 0.1A g -1 Exhibit up to 230mAh g at current densities of -1 And the charge-discharge voltage plateau corresponds to the redox peak potential of the cyclic voltammetry curve. The rate capability test of FIG. 9 shows that even at rates as high as 10A g -1 At a current of 114mAh g, the aluminum battery still had -1 The specific capacity of (a). The cycling performance test of fig. 10 shows that the aluminum cell can be stably cycled 60000 times.
Claims (6)
1. A pyrene-dihydrophenazine based conjugated microporous polymer, comprising: the structure of the pyrene-dihydrophenazine-based conjugated microporous polymer is as follows:
2. a method for preparing a pyrene-dihydrophenazine based conjugated microporous polymer according to claim 1, comprising: under the protection of nitrogen, 5,10-dihydrophenazine, 1,3,6,8-tetrabromopyrene, a ligand, a palladium catalyst and sodium tert-butoxide are added into a Schlenk tube, an organic solvent is added, the mixture is heated until reflux reaction is carried out for 24 to 72 hours, the mixture is cooled to room temperature after the reaction is finished, dichloromethane, methanol and water are used for washing, tetrahydrofuran is used for reflux extraction in a Soxhlet extractor, and vacuum drying is carried out, so that the pyrene-dihydrophenazine conjugated microporous polymer is obtained, wherein the reaction equation is as follows:
the ligand is any one of 2-dicyclohexylphosphine-2 ',6' -diisopropoxy-1,1 ' -biphenyl, 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl and tri-tert-butylphosphine;
the palladium catalyst is any one of (2 ' -amino- [1,1' -biphenyl ] -2-yl) (dicyclohexyl (2 ',6' -diisopropoxy- [1,1' -biphenyl ] -2-yl) phosphoryl) palladium chloride, bis (dibenzylideneacetone) palladium and palladium acetate.
3. The method for preparing a pyrene-dihydrophenazine based conjugated microporous polymer according to claim 2, wherein: the molar ratio of 5,10-dihydrophenazine to 1,3,6,8-tetrabromophyrene is 1, and the concentration of 5,10-dihydrophenazine in the organic solvent is controlled to be 0.1-1 mol/L.
4. The method for preparing a pyrene-dihydrophenazine based conjugated microporous polymer according to claim 2, wherein: the addition amount of the ligand is 1-5% of the molar amount of 5,10-dihydrophenazine, the addition amount of the palladium catalyst is 1-5% of the molar amount of 5,10-dihydrophenazine, and the addition amount of the sodium tert-butoxide is 3-7 times of the molar amount of 5,10-dihydrophenazine.
5. The method for preparing a pyrene-dihydrophenazine based conjugated microporous polymer according to claim 2, wherein: the organic solvent is any one of toluene, o-xylene, 1,4-dioxane and tetrahydrofuran.
6. Use of the pyrene-dihydrophenazine based conjugated microporous polymer according to claim 1 as an anode active material for an aluminum battery.
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| CN111848951A (en) * | 2020-08-12 | 2020-10-30 | 台州学院 | Conjugated organic polymer based on 1,3,6, 8-tetra (4-aminophenyl) pyrene and preparation method thereof |
| CN112300371A (en) * | 2020-10-28 | 2021-02-02 | 苏州大学 | Polymer based on phenazine tripolymer, preparation method and battery application thereof |
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| CN111848951A (en) * | 2020-08-12 | 2020-10-30 | 台州学院 | Conjugated organic polymer based on 1,3,6, 8-tetra (4-aminophenyl) pyrene and preparation method thereof |
| CN112300371A (en) * | 2020-10-28 | 2021-02-02 | 苏州大学 | Polymer based on phenazine tripolymer, preparation method and battery application thereof |
Non-Patent Citations (2)
| Title |
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| MA WJ等: "Toward High-Performance Dihydrophenazine-Based Conjugated Microporous Polymer Cathodes for Dual-Ion Batteries through Donor–Acceptor Structural Design", 《ADV. FUNCT. MATER.》, vol. 31, pages 1 - 9 * |
| ZHAO YANG等: "Porous carbons derived from pyrene-based conjugated microporous polymer for supercapacitors", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 240, pages 73 - 79, XP029919194, DOI: 10.1016/j.micromeso.2016.10.048 * |
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