CN114920930A - Pyrazine-benzoquinone structure-containing polymer and application thereof in lithium ion/water-based zinc ion battery - Google Patents
Pyrazine-benzoquinone structure-containing polymer and application thereof in lithium ion/water-based zinc ion battery Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 75
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- IBAUUODWKROETE-UHFFFAOYSA-N N1=CC=NC=C1.C1(C=CC(C=C1)=O)=O Chemical group N1=CC=NC=C1.C1(C=CC(C=C1)=O)=O IBAUUODWKROETE-UHFFFAOYSA-N 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 12
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 89
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- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 12
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- 238000001816 cooling Methods 0.000 claims description 6
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- DNHCPEFCQYRQQN-UHFFFAOYSA-N 2,3,5,6-tetraaminocyclohexa-2,5-diene-1,4-dione Chemical compound NC1=C(N)C(=O)C(N)=C(N)C1=O DNHCPEFCQYRQQN-UHFFFAOYSA-N 0.000 claims description 5
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
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- ZYOYYQRWXITKFF-UHFFFAOYSA-N pyrazine-2,3-dione Chemical group O=C1N=CC=NC1=O ZYOYYQRWXITKFF-UHFFFAOYSA-N 0.000 claims 1
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- 238000012360 testing method Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
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- 239000002033 PVDF binder Substances 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 230000037427 ion transport Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a polymer containing a pyrazine-benzoquinone structure and application thereof in a lithium ion/water system zinc ion battery. The conjugated structure not only makes the charges delocalized between adjacent molecules, thereby improving the stability of charge and discharge; the charge delocalization enhances the intermolecular interaction, which is favorable for charge transfer; and the formed laminated structure is expected to form rapid ion transportation. The pyrene ketone-benzoquinone polymer not only ensures higher theoretical capacity, but also ensures high conductivity of the polymer, and further improves the electrochemical performance of the material. When the pyrene ketone-benzoquinone polymer is used as a positive electrode material of a lithium ion battery and a water-based zinc ion battery, the pyrene ketone-benzoquinone polymer shows excellent long cycle life and higher reversible cycle capacity.
Description
Technical Field
The invention relates to a polymer containing a pyrazine-benzoquinone structure and application thereof in a lithium ion/water system zinc ion battery, belonging to the field of metal ion battery electrode materials.
Background
As innovative energy storage solutions are needed due to the steady increase in global energy usage and the shift to renewable energy, people are increasingly interested in the development of various battery technologies, and in order to meet the demand for energy storage, energy density, stability and safety need to be improved. LIBs, as an energy storage technology with great development prospect, has the advantages of zero memory effect, high energy density, low self-discharge and the like and excellent comprehensive performance, so that LIBs becomes an ideal energy storage technology. Further, natural resources (such as minerals of nickel, cobalt, manganese, etc.) are excessively consumed, so that resource exhaustion and environmental pollution are caused, and the development of secondary batteries is limited. The development of novel high-capacity, low-cost, high-stability, green and safe electrode materials is urgently needed.
Compared with the traditional inorganic materials, the organic electrode material is composed of abundant elements (C, H, O, N and S), has high structural designability and low environmental pollution and toxicity, can be produced by more environment-friendly procedures, and only needs a recovery process with lower energy consumption. The organic electrode material has chemical bond rearrangement in the oxidation-reduction process, can effectively avoid larger structural change, quickens reaction kinetics, is favorable for improving structural stability and electrochemical performance, and becomes an active electrode material with great prospect.
However, most organic electrode materials and their intermediates or charge and discharge products are very soluble in the electrolyte, and the conductivity of the organic electrode material is too low, resulting in low cycling stability and poor cycle life of the organic electrode material. Researches find that the conjugated structure is beneficial to enhancing the interaction between molecules, thereby accelerating the transfer of charges and improving the conductivity; the pi conjugated system is beneficial to improving the microstructure of the organic material, such as forming a lamellar structure, and is expected to form a rapid ion channel; meanwhile, the formed long polymer chains also effectively reduce the solubility of the active material in the electrolyte. Secondly, the molecular structure of the organic polymer has certain flexibility and only accompanies the rearrangement of chemical bonds in the redox process, thereby effectively avoiding larger structural change. Thereby obtaining an organic electrode material with high reversible capacity and long cycle life.
Disclosure of Invention
The invention provides a polymer containing a pyrazine-benzoquinone structure and application thereof in a lithium ion/water-based zinc ion battery aiming at providing an electrode material containing a multi-active conjugated organic polymer to realize high reversible capacity, excellent cycling stability and other electrochemical performances.
The polymer containing the pyrazine-benzoquinone structure has the following structural general formula:
the invention relates to a synthesis method of a polymer containing a pyrazine-benzoquinone structure, which comprises the following steps:
step 1: weighing 2,3,5, 6-tetraaminop-benzoquinone and pyrene-4, 5,9, 10-tetraone, adding into thick-wall reaction tube containing 5.0ml of N-methylpyrrolidone, and reacting at normal temperature under N condition 2 Stirring for 30min under the atmosphere condition, then reacting the reaction tube at 80 ℃ for more than 15h, and then heating to 130 ℃ to react for 10h to generate black solid.
Step 2: stopping the reaction, cooling to room temperature, adding pyrene-4, 5,9, 10-tetraketone into the reaction tube again, reacting for 5 hours at 180 ℃, and generating a large amount of black solid after full reaction; and cooling to room temperature after the reaction is finished, collecting black solid by centrifugation, performing multiple times of centrifugal washing by tetrahydrofuran, and finally performing vacuum drying to obtain the black solid.
And 3, step 3: purifying by a Soxhlet extraction method, extracting with an organic solvent until the solvent is colorless, washing, and finally drying in vacuum at 140 ℃ for 20 hours to obtain a final product, namely the pyreneketone-benzoquinone polymer.
In the step 1, the feeding molar ratio of pyrene-4, 5,9, 10-tetraketone and 2,3,5, 6-tetraaminop-benzoquinone is 1.05-1.15: 1.
In the step 2, the ratio of the molar weight of the pyrene-4, 5,9, 10-tetraone to the molar weight of the pyrene-4, 5,9, 10-tetraone in the step 1 is 0.05: 1.
In step 3, organic solvent dichloromethane extraction (extraction at 50-60 ℃ for at least four hours) and tetrahydrofuran solvent extraction (extraction at 70-80 ℃ for at least five hours) are respectively adopted until the mother liquor is colorless.
The reaction scheme is as follows:
the application of the polymer containing the pyrazine-benzoquinone structure is to use the polymer containing the pyrazine-benzoquinone structure as a positive electrode material of a metal lithium ion battery or a water-based zinc ion battery.
Specifically, a polymer containing a pyrazine-benzoquinone structure is taken as an active material, mixed with an adhesive and a conductive agent in an organic solvent, coated on an aluminum foil or a titanium foil, dried in vacuum at 80-100 ℃ for more than 12h, and cut to prepare a positive electrode plate; and (3) assembling the lithium ion/water system zinc ion battery by taking metal lithium or zinc as a negative electrode and a diaphragm and adding an electrolyte.
The invention has the following beneficial effects:
the synthesis method of the pyrene ketone-benzoquinone polymer electrode material is simple, and the pyrene ketone-benzoquinone polymer electrode material has multiple active sites (C-N, C-O), so that higher cycle capacity is ensured; the conjugated structure is favorable for enhancing the interaction between molecules, thereby accelerating the transfer of charges and improving the conductivity; the pi conjugated system is beneficial to improving the microstructure of the organic material, such as forming a lamellar structure, and is expected to form a rapid ion channel; meanwhile, the formed long polymer chains also effectively reduce the solubility of the active material in the electrolyte. Secondly, the molecular structure of the organic polymer has certain flexibility and only accompanies the rearrangement of chemical bonds in the redox process, thereby effectively avoiding larger structural change. Therefore, the organic polymer electrode material can realize higher energy density, rate capability and excellent cycling stability.
Drawings
FIG. 1 is a scanning photograph of a pyrene ketone-benzoquinone polymer according to example 1 of the present invention;
FIG. 2 is a transmission photograph of a pyrene ketone-benzoquinone polymer according to example 1 of the present invention;
FIG. 3 is a thermogravimetric plot of a pyrene ketone-benzoquinone polymer of example 1 of the present invention;
FIG. 4 is an IR spectrum of a pyrene ketone-benzoquinone polymer and starting material according to example 1 of the present invention;
FIG. 5 shows that the sweep rate of the pyrene ketone-benzoquinone polymer as a lithium ion battery cathode material in example 1 of the present invention is 0.1mVs -1 Graph of CV of (a);
FIG. 6 shows that the pyrene ketone-benzoquinone polymer of example 1 of the present invention has a current density of 0.2Ag -1 A time lithium ion battery charging and discharging curve chart;
FIG. 7 shows that the pyrene ketone-benzoquinone polymer of example 1 has a current density of 0.2Ag -1 A time lithium ion battery cycle performance diagram;
FIG. 8 is a graph showing the rate capability of a lithium ion battery with a pyrene ketone-benzoquinone polymer according to example 1 under different current densities;
FIG. 9 shows that the pyrene ketone-benzoquinone polymer of example 1 of the present invention has a current density of 5.0Ag -1 A long cycle performance diagram of the lithium ion battery;
FIG. 10 shows a graph of the current density of 0.1Ag for the pyrene ketone-benzoquinone polymer of example 1 of the present invention -1 A time zinc ion battery charge-discharge curve;
FIG. 11 shows a pyrene ketone-benzoquinone polymer having a current density of 0.1Ag in example 1 of the present invention -1 A time zinc ion battery cycle performance diagram;
FIG. 12 is a graph showing the rate capability of a zinc ion battery of the pyrene ketone-benzoquinone polymer of example 1 of the present invention at different current densities;
FIG. 13 shows the relationship between the current density of the pyrene ketone-benzoquinone polymer of example 1 of the present invention and the current density of the pyrene ketone-benzoquinone polymer at 2.0Ag -1 Long cycle of zinc ion batteryAnd (6) performance graphs.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The experimental methods used in the following examples are all conventional methods unless otherwise specified.
Reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The performance test of the batteries in the following examples adopts a Xinwei battery test system, the positive electrode material, Keqin black and a binder (PVDF) obtained in the following examples are uniformly mixed in a solvent NMP according to the mass ratio of 60:30:10 to prepare slurry, then the slurry is uniformly coated on an aluminum foil or titanium foil current collector to prepare a working electrode, a lithium battery diaphragm is polypropylene/polyethylene (PP/PE), a lithium battery electrolyte is 1MLiTFSI solution (purchased from the market) of DME/DOL (volume ratio of 1:1), and the solution is assembled into a 2032 button battery in an argon-filled glove box, wherein the test voltage range is 1.2V-3.8V vs Li + and/Li. The water system zinc ion battery diaphragm is a glass fiber diaphragm; the electrolyte is 2MZnSO 4 Assembling 2032 type button cell in air with water solution, and testing voltage range is 0.3V-1.6VvsZn 2 + /Zn。
The embodiment is as follows:
step 1: weighing 2,3,5, 6-tetraaminobenzoquinone 1mmol and pyrene-4, 5,9, 10-tetraone 1.05mmol, adding into a thick-walled reaction tube containing N-methylpyrrolidone 5.0ml, and reacting at normal temperature under N 2 Stirring for 30min under the atmosphere condition, then reacting the reaction tube at 80 ℃ for more than 15h, and then heating to 130 ℃ to react for 10h to generate black solid.
Step 2: stopping the reaction, cooling to room temperature, adding 10.0mg of pyrene tetrone into the reaction tube again, reacting for 5 hours at 180 ℃, and generating a large amount of black solid after full reaction; and cooling to room temperature after the reaction is finished, collecting a black solid through centrifugation, performing multiple times of centrifugal washing by using tetrahydrofuran, and finally performing vacuum drying to obtain the black solid.
And step 3: purifying by adopting a Soxhlet extraction mode, extracting by adopting an organic solvent until the solvent is colorless, washing, and finally drying in vacuum at 140 ℃ for 20 hours to obtain a final product, namely the pyrene ketone-benzoquinone polymer.
FIGS. 1 and 2 are a scanning photograph and a transmission photograph of the pyrene ketone-quinone polymer obtained in example 1, respectively, wherein the polymer exhibits a disordered stacking state, and the transmission image shows that the microstructure of the polymer exhibits a layered stack and a large number of white dots exist, indicating that the polymer has a uniformly distributed pore structure.
FIG. 3 is a thermogravimetric curve of the pyrene ketone-benzoquinone polymer of example 1 of the present invention, wherein thermogravimetric analysis was performed in air and nitrogen atmosphere to investigate the thermal stability of the polymer, and the curve shows no weight loss before 200 ℃ and a faster mass loss after 300 ℃, indicating that the polymer has better thermal stability. When heated in air, carbon reacts with air to generate carbon dioxide gas, and no mass is left. The material is completely decomposed and carbonized by heating to 900 ℃ under nitrogen, and the polymer is proved to have larger molecular weight.
FIG. 4 is an IR spectrum comparison of a pyrene ketone-benzoquinone polymer and a raw material according to example 1 of the present invention, and the chemical composition of the pyrene ketone-benzoquinone polymer was investigated by FT-IR. FIG. 4 shows the corresponding functional groups for the polymer and the starting material, with C ═ O (1680 cm) in the spectra for all three materials -1 ) The stretching vibration peaks of the double bonds are derived from the C ═ O double bond in the pyrene tetraone and the C ═ O in the anthraquinone ring, respectively, and the stretching vibration peaks of the C ═ O are also present in the pyrene ketone-benzoquinone polymer produced after the complete reaction, and are derived from the C ═ O which does not participate in the reaction in the anthraquinone ring. Two peaks C ═ N which are not present in the starting materials appear in the polymer, and-NH derived from tetraaminop-benzoquinone 2 And C-N double bonds generated by condensation polymerization reaction of C-O in pyrene tetraketone. Wherein, the infrared spectrogram of the raw material tetraaminobenzoquinone is 3323cm -1 And 3428cm -1 The two peaks are derived from-NH 2 The symmetric stretching vibration and the asymmetric stretching vibration disappear from the spectrum of the pyrene ketone-benzoquinone polymer, and the fact that-NH is not contained in the polymer is shown 2 The existence of (b) further indicates that the reaction is relatively thorough. Meanwhile, the intrinsic structures of the PT unit and the TABQ unit can be proved to be well maintained in the polymer through comparison of infrared spectrums.
FIG. 5 shows that the sweep rate of the pyrene ketone-benzoquinone polymer as a lithium ion battery cathode material in example 1 of the present invention is 0.1mVs -1 Graph of CV of (a); a broad peak is observed in the CV curve, involving multiple redox reactions, indicating that both the C ═ O and newly formed C ═ N double bonds in the benzoquinone unit are active groups capable of binding to lithium ions. In the subsequent cycle, the CV curve shows a highly coincident trend, which indicates that the pyrene ketone-benzoquinone polymer has a stable conjugated skeleton and can effectively maintain reversible redox reaction.
FIG. 6 shows that the pyrene ketone-benzoquinone polymer of example 1 of the present invention has a current density of 0.2Ag -1 A time lithium ion battery charging and discharging curve chart; the coincidence of the charge and discharge curves is a platform because the two pairs of redox peaks are very close. Its charge and discharge plateau was at 2.47V and showed higher capacity.
FIG. 7 shows a graph of the current density of 0.2Ag for the pyrene ketone-benzoquinone polymer of example 1 of the present invention -1 A time lithium ion battery cycle performance diagram; the pyrene ketone-benzoquinone polymer electrode material has higher initial discharge capacity 323mAg -1 And the material has high initial coulombic efficiency (more than 85 percent), shows extremely high coulombic efficiency of about 100 percent in later cycles, has very low capacity fading speed, and has good electrochemical stability.
FIG. 8 is a graph showing the rate capability of a lithium ion battery with a positive electrode of the pyrene ketone-benzoquinone polymer at 0.1, 0.2, 0.5, 1.0, 2.0, 5.0A g under different current densities in example 1 of the present invention -1 278, 248, 217, 197, 178 and 154mAh g were obtained, respectively -1 High discharge capacity when the current density returns to the initial 0.1Ag -1 At this time, the discharge capacity still returns to 270mAh g -1 The polymer is proved to have excellent rate performance and maintain excellent reversibility.
FIG. 9 is the presentIn the invention example 1, the pyrene ketone-benzoquinone polymer has a current density of 5.0Ag -1 Long cycle performance diagram of lithium ion battery at 5.0Ag -1 Its initial capacity reaches 160mAh g -1 Can still maintain 118mAh g after 1000 cycles -1 The reversible capacity of (2) shows a capacity loss of only 0.042% per cycle, and shows excellent high-rate cycle performance, which is derived from the fact that the conjugated long chains and the structure in the polymer have excellent electron and ion transport capabilities.
FIG. 10 shows that the pyrene ketone-benzoquinone polymer of example 1 of the present invention has a current density of 0.1Ag -1 The charging and discharging curve of the zinc ion battery shows a relatively obvious charging and discharging platform near 0.85V, and simultaneously shows relatively high reversible capacity.
FIG. 11 shows a pyrene ketone-benzoquinone polymer having a current density of 0.1Ag in example 1 of the present invention -1 The zinc ion battery has the cycle performance that the electrode material is 0.1Ag -1 Has 275mAh g -1 The initial capacity of (a). After 50 cycles, the product still maintains 229mAh g -1 The reversible capacity of (a).
FIG. 12 is a graph showing the rate capability of a zinc ion battery under different current densities of the pyrene ketone-benzoquinone polymer of example 1 of the present invention, wherein the positive electrode of the pyrene ketone-benzoquinone polymer is at 0.1, 0.2, 0.5, 1.0, 2.0, 5.0A g -1 At current densities of 205, 186, 168, 149, 128 and 104mAh g, respectively, were obtained -1 High discharge capacity when the current density returns to the initial 0.1Ag -1 At this time, the discharge capacity still returns to 203mAh g -1 The fact that the pyrene ketone-benzoquinone polymer has excellent rate performance is demonstrated, and the fact that the conjugated structure has excellent conductivity is further proved.
FIG. 13 shows a graph of the current density of 2.0Ag for the pyrene ketone-benzoquinone polymer of example 1 of the present invention -1 Long cycle performance diagram of the lithium ion battery at 2.0Ag -1 Can still maintain 166mAh g after 5000 cycles -1 The reversible capacity of (a). The result shows that the pyrene ketone-benzoquinone polymer still shows excellent cycle stability when being used as the positive electrode of the zinc ion battery, and is benefited by the fact that the pyrene ketone-benzoquinone polymer has higher polymerization degree and conjugated structure.
In conclusion, the pyrazine-containing and benzoquinone polymer prepared by the invention has excellent electrochemical performance when being used as a positive electrode material of a metal lithium ion battery and an aqueous zinc ion battery.
Claims (7)
1. A polymer containing a pyrazine-benzoquinone structure is characterized in that the structure is as follows:
2. a method for synthesizing a polymer containing a pyrazine-quinone structure according to claim 1, comprising the following steps:
step 1: weighing 2,3,5, 6-tetraaminop-benzoquinone and pyrene-4, 5,9, 10-tetraone, adding into a thick-wall reaction tube containing N-methylpyrrolidone, and reacting at normal temperature under the action of N 2 Continuously stirring for 30min under the atmosphere condition, then reacting the reaction tube at 80 ℃ for more than 15h, and then heating to 130 ℃ for reaction for 10h to generate black solids;
and 2, step: stopping the reaction, cooling to room temperature, adding pyrene-4, 5,9, 10-tetraketone into the reaction tube again, reacting for 5 hours at 180 ℃, and generating a large amount of black solid after full reaction; after the reaction is finished, cooling to room temperature, collecting a black solid through centrifugation, centrifugally washing with tetrahydrofuran, and drying in vacuum to obtain a black solid;
and step 3: purifying by adopting a Soxhlet extraction mode, extracting by using an organic solvent until the solvent is colorless, washing, and finally drying in vacuum at 140 ℃ for 20 hours to obtain a final product, namely the pyrene ketone-benzoquinone polymer.
3. The method of synthesis according to claim 2, characterized in that:
in the step 1, the feeding molar ratio of pyrene-4, 5,9, 10-tetraketone and 2,3,5, 6-tetraaminop-benzoquinone is 1.05-1.15: 1.
4. The method of synthesis according to claim 2, characterized in that:
in the step 2, the molar weight ratio of the pyrene-4, 5,9, 10-tetraone to the pyrene-4, 5,9, 10-tetraone is again added to be 0.05: 1.
5. The method of synthesis according to claim 2, characterized in that:
in step 3, the organic solvent is dichloromethane and tetrahydrofuran solvent respectively.
6. Use of a polymer containing a pyrazine-benzoquinone structure according to claim 1, wherein:
the polymer containing the pyrazine-benzoquinone structure is used as a positive electrode material of a metal lithium ion battery or a water-based zinc ion battery.
7. Use according to claim 6, characterized in that:
taking a polymer containing a pyrazine-benzoquinone structure as an active material, placing the active material, a binder and a conductive agent into an organic solvent for mixing, coating the mixture on an aluminum foil or a titanium foil, performing vacuum drying at the temperature of between 80 and 100 ℃ for more than 12 hours, and cutting to prepare a positive electrode piece; and (3) assembling the lithium ion/water system zinc ion battery by taking metal lithium or zinc as a negative electrode and a diaphragm and adding an electrolyte.
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| CN116355230A (en) * | 2023-03-29 | 2023-06-30 | 华中科技大学 | High-conductivity conjugated coordination polymer material and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115505122A (en) * | 2022-10-09 | 2022-12-23 | 南京理工大学 | Imine polymer positive electrode material synthesized by solvent-free method and application thereof |
| CN115505122B (en) * | 2022-10-09 | 2023-12-08 | 南京理工大学 | Imine polymer positive electrode material synthesized by solvent-free method and application thereof |
| CN116355230A (en) * | 2023-03-29 | 2023-06-30 | 华中科技大学 | High-conductivity conjugated coordination polymer material and preparation and application thereof |
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