CN116987087A - High-conjugated pyrazine fused ring compound and application thereof in lithium ion battery - Google Patents
High-conjugated pyrazine fused ring compound and application thereof in lithium ion battery Download PDFInfo
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- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 150000001875 compounds Chemical class 0.000 title claims abstract description 77
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 title claims abstract description 72
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000006482 condensation reaction Methods 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 5
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 5
- IHZVARNFIMXWFZ-UHFFFAOYSA-N piperazine-2,3-diamine Chemical compound N1C(C(NCC1)N)N IHZVARNFIMXWFZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007774 positive electrode material Substances 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-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
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 2
- 150000003384 small molecules Chemical class 0.000 description 27
- 238000009792 diffusion process Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- -1 Pyrene-4,5,9, 10-tetraone (Pyrene-4, 5,9, 10-tetrone) Chemical compound 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a high-conjugated pyrazine fused ring compound and application thereof in a lithium ion battery, wherein the Gao Gonge pyrazine fused ring compound is prepared from pyrene-4,5,9, 10-tetraketone and 2, 3-diaminopiperazine through a dehydration condensation reaction, and the structure is shown as follows:the high conjugated pyrazine fused ring compound is applied to a lithium ion battery anode material, successfully solves the electrochemical stability problem caused by the high solubility of the traditional small organic molecules, and realizes the capacity (236.35 mAhg ‑1 ) Circulation stability and multiplying power performance10Ag ‑1 The current density is cycled for 2000 circles, and the capacity is kept at 87.49mAhg ‑1 ) Is significantly improved.
Description
Technical Field
The invention relates to a high conjugated pyrazine fused ring compound (pyrazino [2,3-b ] pyrazino [2',3': 5',6' ] pyrazino [2',3':9,10] phenanthrene [4,5-fgh ] quinoxaline) and application thereof in lithium ion batteries, and belongs to the field of lithium ion battery electrode materials.
Background
With the continuous rise of energy demand, energy storage technologies face new opportunities and challenges, and the development of high-performance and sustainable energy storage devices is becoming a research hotspot today. Currently, lithium Ion Batteries (LIBs) have been applied to numerous energy storage fields and dominate the energy storage market by virtue of their excellent properties in various aspects. However, the commercial positive electrode materials of LIBs are mostly inorganic materials, such as transition metal oxides (LiCoO) 2 And LiFePO 4 ) They are limited by low specific capacity, limited raw material resources, safety, recycling, etc. In contrast, organic electrode materials, which consist of abundant and lightweight elements (C, H, O, N and S, etc.), high specific capacities, have proven to be potential candidates for the next generation. In addition, the organic compound can exhibit rapid reaction kinetics and excellent ion storage behavior due to the high number of surface-exposed electroactive groups and weak intermolecular interaction forces. However, the problems of the organic electrode material, such as easy dissolution and low conductivity, are not ignored, and the problems prevent the application of the organic electrode material in a metal battery.
It was found that organic compounds based on c=n bonds exhibit excellent electrochemical properties in lithium ion battery cathode materials. During discharge, the c=n double bond reacts with the metal ion to form a "conjugated double bond lithium storage". In addition, a large number of pi conjugated units are beneficial to rapid charge transmission and collection, and the stability of the structure can be improved in the charge-discharge process. The high conjugated pyrazine fused ring compound is used as an organic small molecule positive electrode material, is introduced into a pi conjugated system containing a plurality of C=N bonds, has more active sites, and can greatly increase theoretical capacity. Meanwhile, the lone pair electron of the C=N bond endows the compound with higher redox activity, and higher cycle specific capacity is obtained in the lithium ion battery. Finally, a large number of pi conjugated units are beneficial to improving the ion diffusion rate and the electron conductivity in the charge and discharge process, enhancing the intermolecular acting force and reducing the solubility of organic compounds, so that good electrochemical cycling stability and rate capability are realized in the lithium ion battery.
Disclosure of Invention
The invention aims to provide a high conjugated pyrazine fused ring compound (pyrazino [2,3-b ] pyrazino [2',3': 5',6' ] pyrazino [2',3':9,10] phenanthrene [4,5-fgh ] quinoxaline) and application thereof in lithium ion batteries. The high-conjugated pyrazine fused ring compound is applied to a lithium ion battery anode material, and has higher battery capacity (236.35 mAh/g), cycle stability and rate capability (after 2000 cycles at 10A/g current density, the capacity is kept at 87.49 mAh/g), and excellent electrochemical performance.
The high conjugated pyrazine fused ring compound is obtained by a dehydration condensation reaction of pyrene-4,5,9, 10-tetraketone and 2, 3-diaminopiperazine, and has the following structure:
the high conjugated pyrazine fused ring compound is prepared by the following steps:
25-27mg of Pyrene-4,5,9, 10-tetraone (Pyrene-4, 5,9, 10-tetrone) and 54-56mg of 2, 3-diaminopiperazine (2, 3-diaminopiperazine) were weighed, placed in 23-27mL of acetic acid, and heated and stirred at 145 ℃ for 40h under argon atmosphere; and after the reaction is finished, washing the mixture by using water, ethanol and dichloromethane, and finally, drying the mixture in vacuum at 80 ℃ for 24 hours to obtain a target product, namely the high conjugated pyrazine fused ring compound.
The application of the high-conjugated pyrazine fused ring compound provided by the invention is that the Gao Gonge pyrazine fused ring compound is used as a positive electrode material of a lithium ion battery.
The preparation method of the battery comprises the following steps: grinding the high conjugated pyrazine fused ring compound organic micromolecular positive electrode material, the conductive carbon material and the cross-linking agent into slurry in an organic solvent, coating the slurry on an aluminum foil current collector, and carrying out vacuum drying at 80-100 ℃ for 20-26 hours to prepare the positive electrode plate. And (3) taking a metal lithium sheet as a negative electrode, separating two electrodes by using a diaphragm, adding electrolyte, and assembling the button cell in a glove box filled with argon.
Further, the electrolyte is a 1.0M lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) solution (commercially available) containing ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL) (volume ratio 1:1); the conductive carbon material is ketjen black; the cross-linking agent is polyvinylidene fluoride (PVDF).
The organic micromolecule positive electrode material is applied to a lithium ion battery positive electrode material, and is favorable for realizing better electrochemical cycling stability and multiplying power performance of the battery due to the fact that the organic micromolecule positive electrode material contains a large amount of pi conjugated structures. A large number of C=N bonds are used as redox active sites, so that the density of the redox active sites is improved, the redox active sites are coordinated with lithium ions in a synergistic manner, the reversible storage of the lithium ions is realized, the higher circulation specific capacity is shown, and the electrochemical performance is excellent.
Compared with the prior art, the invention has the beneficial effects that:
1. the high-conjugated pyrazine fused ring compound organic micromolecule positive electrode material is prepared by one-step dehydration condensation reaction and repeated purification, the preparation method of the product is simple, the used raw materials are environment-friendly, the high-conjugated pyrazine fused ring compound organic micromolecule positive electrode material is applied to a lithium ion battery, has higher capacity (236.35 mAh/g), cycle stability and rate capability (after 2000 circles of cycle under 10A/g current density, the capacity is kept at 87.49 mAh/g), the capacity of the traditional micromolecule electrode material is obviously improved, and the high-conjugated pyrazine fused ring compound organic micromolecule positive electrode material has excellent electrochemical performance.
2. The high conjugated pyrazine fused ring compound is an electron-withdrawing, rigid and planar aromatic disk-shaped molecule, is designed and introduced into a pi conjugated system containing a large number of C=N bonds, provides as many active sites as possible, and increases theoretical capacity. In addition, in the charge-discharge process, a large number of pi conjugated units are beneficial to rapid charge transmission and collection, and the ion diffusion rate and the electron conductivity are improved. Meanwhile, the lone pair electron of C=N bond enables the organic small molecule to have higher redox activity, so that higher cycle specific capacity and good rate capability are obtained in the lithium ion battery.
Drawings
Fig. 1 is a schematic diagram of a synthetic route of a high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained by the embodiment of the invention.
Fig. 2 and 3 are scanning photographs of the organic small molecule positive electrode material of the high conjugated pyrazine fused ring compound obtained in the embodiment of the invention after initial and circulation for 300 circles.
Fig. 4 and 5 are elemental mapping images of carbon and nitrogen of a high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained in the embodiment of the invention.
FIG. 6 is a graph showing the comparison of the absorbance of a high conjugated pyrazine fused ring compound organic small molecule positive electrode material and pyrene-4,5,9, 10-tetraketone obtained in the embodiment of the invention.
Fig. 7 is a fourier transform infrared spectrum of a high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained in the embodiment of the invention.
FIG. 8 is a thermogravimetric analysis chart of the organic small molecule positive electrode material of the high conjugated pyrazine fused ring compound obtained by the embodiment of the invention.
FIG. 9 is an electrochemical cycle diagram of a lithium ion battery with a 10A/g current density of the high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained in the embodiment of the invention.
FIG. 10 is a cyclic voltammogram of a lithium ion battery of the high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained in the embodiment of the invention under different scanning rates of 0.2mV/s-2.0 mV/s.
FIG. 11 is a graph showing constant current charge and discharge of a lithium ion battery at a current density of 0.1A/g and different cycle numbers of the high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained by the embodiment of the invention.
FIG. 12 is a graph showing the rate performance of the high conjugated pyrazine fused ring compound organic small molecule positive electrode material and pyrene-4,5,9, 10-tetraketone obtained in the embodiment of the invention under different current densities.
Fig. 13 and 14 are graphs showing comparison of lithium ion diffusion coefficients of the high conjugated pyrazine fused ring compound organic small molecule positive electrode material and pyrene-4,5,9, 10-tetraketone obtained in the embodiment of the invention under different charge and discharge states.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
The experimental methods used in the examples below are conventional, unless otherwise specified.
Reagents, materials, and the like used in the following examples were obtained commercially unless otherwise specified.
The battery performance test in the examples below used a new wife battery test system and a prinston electrochemical workstation.
Example 1:
step 1: 26.22mg of Pyrene-4,5,9, 10-tetraone (Pyrene-4, 5,9, 10-tetrone) and 55.06mg of 2, 3-diaminopiperazine (2, 3-diaminopiperazine) were weighed into a three-necked flask (250 mL) containing 25mL of acetic acid, and heated and stirred under argon atmosphere at 145℃for 40 hours;
step 2: after the reaction is finished, washing with water, ethanol and dichloromethane respectively, and finally drying in vacuum at 80 ℃ for 24 hours to obtain a target product, namely the high conjugated pyrazine fused ring compound.
Example 2:
the positive electrode material, ketjen black and polyvinylidene fluoride (PVDF) obtained in the above example were uniformly mixed with a small amount of N-methyl-2-pyrrolidone (NMP) in a mass ratio of 60:30:10, uniformly ground in an agate mortar to form a well-dispersed slurry, then uniformly coated on an aluminum foil current collector, and vacuum-dried at 100 ℃ for 24 hours to prepare a working electrode. The working electrode is used as an anode plate, the metal lithium sheet is used as a cathode, the diaphragm is an organic diaphragm, the electrolyte is 1M lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) solution (commercially available) containing ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL) (volume ratio 1:1), the 2032 button cell is assembled in a glove box filled with argon, and the test voltage range is 1.2V-3.8V vs Li/Li + 。
Fig. 1 is a schematic diagram of a synthetic route of a high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained by a one-step dehydration condensation reaction and multiple purification preparation, and the preparation method of the product is simple, and the raw materials are environment-friendly.
Fig. 2 and 3 are scanning photographs of the organic small molecule positive electrode material of the high conjugated pyrazine fused ring compound obtained in the embodiment of the invention after initial and circulation for 300 circles. It is clear from the figure that in the initial state, a large number of pores exist on the surface of the high conjugated pyrazine fused ring compound, which is beneficial to the transportation of ions. After 300 times of circulation, the appearance of the high conjugated pyrazine fused ring compound organic small molecule positive electrode material is basically kept similar to the initial appearance, and a large number of pores still exist on the surface to reflect the stability of the structure before and after the circulation.
Fig. 4 and 5 are elemental mapping images of carbon and nitrogen of a high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained in the embodiment of the invention. The uniform distribution of carbon and nitrogen further shows that the high conjugated pyrazine fused ring compound organic small molecule positive electrode material has good component stability before and after circulation.
FIG. 6 is a graph showing the comparison of the absorbance of a high conjugated pyrazine fused ring compound organic small molecule positive electrode material and pyrene-4,5,9, 10-tetraketone obtained in the embodiment of the invention. As shown by comparison in the graph, in the wavelength range of 200-500nm, the absorbance of the high-conjugated pyrazine fused ring compound is lower than that of pyrene-4,5,9, 10-tetraketone, which can indicate that the high-conjugated pyrazine fused ring compound has higher stability and better insolubility in electrolyte due to a unique conjugated structure.
Fig. 7 is a fourier transform infrared spectrum of a high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained in the embodiment of the invention. In the figure, 1675cm of pyrene-4,5,9, 10-tetraketone can be found -1 There appears a distinct peak due to the stretching vibration of the carbonyl group (c=o), 2, 3-diaminopiperazine 3322cm -1 There appears a distinct peak due to the amino group (-NH) 2 ) And about 1600cm on a highly conjugated pyrazine fused ring compound -1 Where occursA distinct peak, due to stretching vibration of the carbon-nitrogen double bond (c=n). By contrast, the disappearance of carbonyl and amino groups in the highly conjugated pyrazine fused ring compound, and the appearance of carbon-nitrogen double bonds, can illustrate the successful synthesis of the reaction.
FIG. 8 is a thermogravimetric analysis chart of the organic small molecule positive electrode material of the high conjugated pyrazine fused ring compound obtained by the embodiment of the invention. The pyrene-4,5,9, 10-tetraketone is almost completely decomposed at about 350 ℃, and the high conjugated pyrazine fused ring compound still has good thermal stability at 350 ℃ and basically does not decompose. The decomposition temperature of the high-conjugated pyrazine fused ring compound is about 580 ℃, which can indicate that the high-conjugated pyrazine fused ring compound has good thermal stability, and the high-conjugated pyrazine fused ring compound still has high safety performance at higher temperature when being used as an active electrochemical material of a rechargeable battery.
FIG. 9 is an electrochemical cycle diagram of a lithium ion battery with a 10A/g current density of the high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained in the embodiment of the invention. Even at a higher current density of 10A/g, after 2000 cycles, the discharge specific capacity of the high-conjugated pyrazine fused ring compound still has 87.49mAh/g, the coulomb efficiency is close to 100%, and the specific capacity decays slowly, which indicates that the high-conjugated pyrazine fused ring compound has excellent long cycle performance.
FIG. 10 is a cyclic voltammogram of a lithium ion battery of the high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained in the embodiment of the invention under different scanning rates of 0.2mV/s-2.0 mV/s. The positions and shapes of the oxidation peak and the reduction peak are hardly changed when the scanning rate (0.2 mV/s-2.0 mV/s) of the high-conjugated pyrazine fused ring compound is increased, which shows that the high-conjugated pyrazine fused ring compound has good stability and good reversibility.
FIG. 11 is a graph showing constant current charge and discharge of a lithium ion battery at a current density of 0.1A/g and different cycle numbers of the high conjugated pyrazine fused ring compound organic small molecule positive electrode material obtained by the embodiment of the invention. By comparing the charge-discharge curves of three circles, the shape of the compound is basically unchanged, the specific capacity of the compound decays slowly, and meanwhile, the compound has a higher voltage platform, and the compound can be in one-to-one correspondence with the battery cyclic voltammogram curve of the high conjugated pyrazine fused ring compound. Further, the high conjugated pyrazine fused ring compound has excellent electrochemical performance.
FIG. 12 is a graph showing the rate performance of the high conjugated pyrazine fused ring compound organic small molecule positive electrode material and pyrene-4,5,9, 10-tetraketone obtained in the embodiment of the invention under different current densities. The high conjugated pyrazine condensed ring compound respectively obtains the specific discharge capacities of 236.35, 199.86, 172.53, 153.17, 130.17 and 114.06mAh/g at the current densities of 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0A/g, the specific discharge capacity still has 97.82mAh/g even at the current density of 10A/g, and pyrene-4,5,9, 10-tetraketone has quicker specific capacity attenuation under the current density gradient, and the multiplying power performance is lower than that of the high conjugated pyrazine condensed ring compound, thus indicating the excellent cycle performance of the high conjugated pyrazine condensed ring compound.
Fig. 13 and 14 are graphs showing comparison of lithium ion diffusion coefficients of the high conjugated pyrazine fused ring compound organic small molecule positive electrode material and pyrene-4,5,9, 10-tetraketone obtained in the embodiment of the invention under different charge and discharge states. The diffusion coefficient of lithium ion of the high conjugated pyrazine fused ring compound under different charge and discharge states is in the range of 6.38 multiplied by 10 -11 -8.60×10 -10 cm 2 The diffusion coefficient of/s pyrene-4,5,9, 10-tetraketone ranges from 8.31X10 -13 -7.72×10 -10 cm 2 And/s, which is far lower than the high conjugated pyrazine fused ring compound. The higher ion diffusion coefficient is beneficial to improving the multiplying power performance of the material, which proves that the problem of solubility of pyrene-4,5,9, 10-tetraketone in electrolyte is solved through simple polymerization, and the ion diffusion rate is effectively improved by introducing new active sites and increasing conjugation degree.
In conclusion, the high-conjugated pyrazine fused ring compound organic small molecule positive electrode material prepared by the invention shows excellent electrochemical performance when being applied to a lithium ion battery positive electrode material.
Claims (5)
1. A highly conjugated pyrazine fused ring compound characterized in that:
the Gao Gonge pyrazine fused ring compound is obtained by a dehydration condensation reaction of pyrene-4,5,9, 10-tetraketone and 2, 3-diaminopiperazine, and has the following structure:
2. the highly conjugated pyrazine fused ring compound according to claim 1, characterized by being prepared by a method comprising the following steps:
weighing 25-27mg of pyrene-4,5,9, 10-tetraketone and 54-56mg of 2, 3-diaminopiperazine, placing in 23-27mL of acetic acid, heating and stirring for 40h at 145 ℃ in an argon atmosphere; and after the reaction is finished, washing the mixture by using water, ethanol and dichloromethane, and finally, drying the mixture in vacuum at 80 ℃ to obtain a target product, namely the high conjugated pyrazine fused ring compound.
3. Use of the highly conjugated pyrazine fused ring compound of claim 1, characterized in that:
the Gao Gonge pyrazine fused ring compound is used as a positive electrode material of a lithium ion battery.
4. A use according to claim 3, characterized in that:
grinding the Gao Gonge pyrazine fused ring compound, the conductive carbon material and the cross-linking agent into slurry in an organic solvent, uniformly coating the slurry on an aluminum foil current collector, and carrying out vacuum drying at 80-100 ℃ to prepare a positive electrode plate; and (3) taking a metal lithium sheet as a negative electrode, separating two electrodes by using a diaphragm, adding electrolyte, and assembling the button cell in a glove box filled with argon.
5. The use according to claim 4, characterized in that:
the conductive carbon material is ketjen black; the cross-linking agent is polyvinylidene fluoride; the organic solvent is N-methyl-2-pyrrolidone; the electrolyte is a lithium bis (trifluoromethylsulfonyl) imide solution with the concentration of 1.0M, and the solvent is composed of ethylene glycol dimethyl ether and 1, 3-dioxolane according to the volume ratio of 1:1.
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