CN109020982A - Two quinoxaline phenazene derivatives and its synthetic method and application - Google Patents
Two quinoxaline phenazene derivatives and its synthetic method and application Download PDFInfo
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- CN109020982A CN109020982A CN201810736957.0A CN201810736957A CN109020982A CN 109020982 A CN109020982 A CN 109020982A CN 201810736957 A CN201810736957 A CN 201810736957A CN 109020982 A CN109020982 A CN 109020982A
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- phenazene
- quinoxaline
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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
- C07D487/12—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 three hetero rings
- C07D487/14—Ortho-condensed systems
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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
- 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
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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
Abstract
The present invention relates to two quinoxaline phenazene derivatives and its synthetic method and applications, belong to the synthesis field of lithium ion battery electrode material.Steps are as follows: being added 2 into reactor under inert gas protection; 3- diaminostilbene; 4- phenyl derivatives and triqunioyl decahydrate, are dissolved in organic solvent, and reaction mixture is made be stirred continuously 6-48 hours in reflux state; after reaction; stop heating, adds water that solid product is precipitated, synthesize to obtain two quinoxaline phenazene derivatives; two quinoxaline phenazene derivatives of synthesis have wide application prospect in lithium ion battery electrode material field.
Description
Technical field
The invention belongs to the synthesis field of lithium ion battery electrode material, in particular to two quinoxaline phenazene derivatives and its
Synthetic method and application.
Background technique
Increase with electric car (EV) and intelligent renewable energy to extensive battery system demand, uses organic material
Expecting the prospect as rechargeable battery electrode becomes more and more attractive.In recent years, it is being related to lithium ion battery both at home and abroad just
Negative electrode material, the research of function electrolyte and application and development are quite active, the purpose is to developing low-cost, high safety, high capacity,
High-power, long-life, environmental-friendly lithium ion battery.
Currently, being based on embedded type metal oxide (such as LiCoO2、LiMn2O4、LiFePO4Deng) lithium ion of positive electrode
Lower (the 100-265Wh kg of the specific energy of battery-1), and metallic cobalt price is more expensive, and reserves are limited.It can not meet Gao Gong in future
The demand of rate, environmental-friendly lithium ion battery.The positive electrode for developing new height ratio capacity is constantly subjected to the very big pass of people
Note.
Compared with inorganic, metal oxide electrode, organic electrode materials have lower environmental pollution, higher safety,
And it can realize the production and processing of ecological efficient.Other than light, organic electrode also has high energy storage capacity, because
Their structure can be designed on a molecular scale to support multiple redox reaction.With appropriately designed functional group
Metal such as sodium of the organic compound to lithium and some rich reserves, magnesium, aluminum and zinc has electroactive.People now after
Electroactive organic is used for supercapacitor by continuous explore, hull cell, water solution chargeable electricity battery, lithium-air battery and
The energy storage systems such as redox flow batteries.
Conducting polymer, organosulfur compound, stable free radical compound and be based on oxalates and quinone/phenates derivative
Organic carbonyl compound be used as the electrode material in lithium/sodium-ion battery.However these organic active compounds are non-
Dissolution in proton electrolyte leads to the rapid decay of its capacity in cyclic process.Come in this regard, various strategies have been proposed
Inhibit the dissolution of organic electrode materials, including electric active molecule is made into redox by being covalently bonded on conducting matrix grain
Reactive compound polymerization, by organic carbonyl compound forming salt.Another challenge that organic electrode materials face is due to organic
The intrinsic conductivity of molecule is low and causes power capacity insufficient.It is pi-conjugated containing hetero atom (such as O, N and S) and lone pair electrons
Aromatic compound shows good redox active, and can be used as the electrode material of rechargeable battery.Wherein, azepine
Ring aromatics, such as Schiff base polymer [Angew.Chem.Int.Ed.2014,53,5341-5345], indigo carmine
[Sci.Rep.2013,4,3650] or pteridine [Nat.Commun.2014,5,5335] etc. are used as electrode material by people
And it is subject to study tour.
In order to develop the lithium ion battery of high-energy and high power density, overcome the intrinsic conductivity of organic molecule is low to ask
Topic needs people's design to have the organic molecule of multiple redox centers and high conductivity.It is partly led by high mobility is organic
Body has the inspiration of pi-conjugated system, and herein, our thinking is that design synthesizes new-two quinoline of azepine ring aromatics
Quinoline phenazene derivative contains multiple electroactive azophenlyene units in such compound, it is possible to provide high-capacity lithium ion battery storage, and it expands
The pi-conjugated system of exhibition is conducive to the transmission of the charge in electrode.The purpose that we work is obtained for energy storage such as lithium ion batteries
The high capacity organic electrode materials of system.
Summary of the invention
The purpose of the present invention is intended to provide a kind of synthetic method of two simple and easy quinoxaline phenazene derivative materials.It should
For method using the raw material being easy to get, high yield has synthesized serial two quinoxaline phenazene derivative materials.This method simple process, cost
Lower, low energy consumption, favorable reproducibility.Such material has wide application prospect in lithium ion battery electrode material field.
Two quinoxaline phenazene derivatives, it is characterised in that: the two quinoxaline phenazene derivative structural formulas are
Wherein, the R is-OCH3、-OC2H5, one of-OH or=O；
Two quinoxaline phenazene derivative structures are as shown in A, B, C or D:
The present invention also provides the synthetic methods of above-mentioned two quinoxalines phenazene derivative, carry out as steps described below:
2,3- diaminostilbene, ten water of 4- phenyl derivatives and triqunioyl is added into reactor under inert gas protection
Object is closed, organic solvent is dissolved in, is stirred continuously reaction mixture in reflux state, the reaction time is 6-48 hours, reaction
After, stop heating, is cooled to room temperature plus solid product is precipitated in water, filter, obtain condensation product.
Synthetic reaction equation according to the present invention is as follows:
Wherein, the molar ratio of 2, the 3- diaminostilbene, 4- phenyl derivatives and triqunioyl decahydrate is 3-4:1.
Wherein, the solvent is acetic acid, formic acid, ethyl alcohol, mass fraction 40%HBr aqueous solution, methylene chloride, trifluoro second
One of acid is a variety of.
Wherein, the inert gas is one of nitrogen or argon gas.
Wherein, 2, the 3- diaminostilbene, 4- phenyl derivatives are 2,3- diaminostilbene, 4- dimethoxy benzene, 2,3-
Diaminostilbene, 4- diethoxybenzene, 2,3- diamino-Pyrogentisinic Acid or 2,3- diamino-are to benzophenone.
The present invention also provides the application of two quinoxaline phenazene derivatives, two quinoxaline phenazene derivatives are organic electrode material
Material is used as the electrode material of lithium ion battery.
Advantages of the present invention: two quinoxaline phenazene derivative materials of the invention, synthetic method craft is simple, at low cost,
Low energy consumption, and favorable reproducibility is had excellent performance.It is molten that two quinoxaline phenazene derivative materials not only can solve active material naphthoquinone derivatives
The problems in electrolyte is solved, is expected to obtain the higher performance of electric conductivity to ensure the quick of electronics in electrochemical reaction process
Transmitting, in lithium ion battery electrode material field, has wide application prospect.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of two quinoxaline azophenlyene of 1,4,7,10,13,16- hexa methoxy；
Fig. 2 is the nuclear-magnetism H spectrogram of two quinoxaline azophenlyene of 1,4,7,10,13,16- hexa methoxy；
Fig. 3 is the nuclear-magnetism C spectrogram of two quinoxaline azophenlyene of 1,4,7,10,13,16- hexa methoxy；
Fig. 4 is the mass spectrogram of two quinoxaline azophenlyene of 1,4,7,10,13,16- hexa methoxy.
Specific embodiment
Below by specific embodiment, the invention will be further described
Embodiment 1
60mL acetic acid is added in the three-necked flask of 100mL, while 2,3- diaminostilbene, 4- dimethoxy benzene is added
(0.756g, 4.5mmol), triqunioyl decahydrate (0.522g, 1.5mmol), makes reaction mixture exist under nitrogen protection
Reflux state is stirred continuously, and the reaction time is 48 hours, after reaction, stops heating, water is added to make brown solid
It being precipitated, collected by suction solid is multiple with water and ethanol washing, 80 DEG C of vacuum drying 6h, obtain compound A:1,4,7,10,13,
Two quinoxaline azophenlyene of 16- hexa methoxy.Fig. 1 is infrared spectrogram, and Fig. 2 is nucleus magnetic hydrogen spectrum figure, and Fig. 3 is nuclear-magnetism carbon spectrogram, and Fig. 4 is
Mass spectrogram.
1H NMR(DMSO,500MHz),δ:7.43(s,6H),4.14(s,18H)
13C NMR(DMSO,500MHz),δ:149.56,143.17,135.58,110.39,56.66
ESI-MS m/z:C30H24N6O6Calculated value: 565.56 [M+H]+:565.25
FT-IR(KBr,cm-1):3,448,1636,1399,1384,1286,577
Embodiment 2
Experimental method is with embodiment 1, only by 2,3- diaminostilbene, 4, and-dimethoxy benzene is changed to 2,3- diaminostilbene,
4 ,-diethoxybenzene (0.892g, 4.5mmol) obtains compound B:1,4,7,10,13,16- six ethyoxyl, two quinoxaline pheno
Piperazine.
Embodiment 3
Experimental method is with embodiment 1, only by 2,3- diaminostilbene, 4, and-dimethoxy benzene is changed to 2,3- diamino-to benzene
Phenol (0.64g, 4.5mmol) obtains compound C:1,4,7,10,13,16- hexahydroxy, two quinoxaline azophenlyene.
Embodiment 4
Experimental method is with embodiment 1, only by 2,3- diaminostilbene, 4, and-dimethoxy benzene is changed to 2,3- diamino-to benzene
Ketone (0.622g, 4.5mmol) obtains compound D:1,4,7,10,13,16- six carbonyl, two quinoxaline azophenlyene.
Claims (8)
1. two quinoxaline phenazene derivatives, which is characterized in that the two quinoxaline phenazene derivative structural formulas are as follows:
Wherein, the R is-OCH3、-OC2H5, one of-OH or=O.
2. a kind of synthetic method of two quinoxalines phenazene derivative according to claim 1, which is characterized in that the conjunction
At method are as follows:
2,3- diaminostilbene is added into reactor under inert gas protection, 4- phenyl derivatives and triqunioyl ten are hydrated
Object is dissolved in organic solvent, and reaction mixture is made to carry out being stirred continuously reaction in reflux state, after reaction, stops heating, cold
But to room temperature, add water that solid product is precipitated, filter, obtain product, as two quinoxaline phenazene derivatives；
Synthetic reaction equation are as follows:
3. the synthetic method of two quinoxalines phenazene derivative according to claim 2, it is characterised in that: 2, the 3- diamino
The molar ratio of base -1,4- phenyl derivatives and triqunioyl decahydrate is 3-4:1.
4. the synthetic method of two quinoxalines phenazene derivative according to claim 2, it is characterised in that: the solvent is
One of acetic acid, formic acid, ethyl alcohol, mass fraction 40%HBr aqueous solution, methylene chloride, trifluoroacetic acid are a variety of.
5. the synthetic method of two quinoxalines phenazene derivative according to claim 2, it is characterised in that: when the described reaction
Between be 6-48 hours.
6. the synthetic method of two quinoxalines phenazene derivative according to claim 2, it is characterised in that: the indifferent gas
Body is one of nitrogen or argon gas.
7. the synthetic method of two quinoxalines phenazene derivative according to claim 2, it is characterised in that: 2, the 3- bis-
Amino -1,4- phenyl derivatives are 2,3- diaminostilbene, 4- dimethoxy benzene, 2,3- diaminostilbene, 4- diethoxybenzene, 2,3-
Diamino-Pyrogentisinic Acid or 2,3- diamino-are to one of benzophenone.
8. a kind of application of two quinoxalines phenazene derivative according to claim 1, it is characterised in that: two quinolines
Application of the quinoline phenazene derivative in the positive electrode of lithium ion battery.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212203A (en) * | 2019-05-22 | 2019-09-06 | 南京大学 | A kind of organic flow battery of basic hydroxide group azophenlyene class and preparation method |
| CN111440179A (en) * | 2020-04-07 | 2020-07-24 | 曲靖师范学院 | Conjugated organic lithium ion battery electrode material and preparation method and application thereof |
| CN112409364A (en) * | 2020-11-11 | 2021-02-26 | 常州大学 | Hexaazanaphthalene derivative and preparation method and application thereof |
| CN112563521A (en) * | 2020-12-01 | 2021-03-26 | 常州大学 | Alkaline water-system mixed liquid flow battery based on electroactive phenazine derivative negative electrode |
| CN113121547A (en) * | 2021-04-08 | 2021-07-16 | 常州大学 | Nitrogen-containing polyquinone organic electrode material and preparation method and application thereof |
| CN114883559A (en) * | 2022-04-29 | 2022-08-09 | 安徽大学 | Naphthoquinone-quinoxaline organic electrode material and application thereof in aqueous zinc ion battery |
| CN115057862A (en) * | 2022-04-29 | 2022-09-16 | 安徽大学 | Pyrazine-quinoxaline organic electrode material and application thereof in lithium ion battery |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212203A (en) * | 2019-05-22 | 2019-09-06 | 南京大学 | A kind of organic flow battery of basic hydroxide group azophenlyene class and preparation method |
| CN111440179A (en) * | 2020-04-07 | 2020-07-24 | 曲靖师范学院 | Conjugated organic lithium ion battery electrode material and preparation method and application thereof |
| CN112409364A (en) * | 2020-11-11 | 2021-02-26 | 常州大学 | Hexaazanaphthalene derivative and preparation method and application thereof |
| CN112563521A (en) * | 2020-12-01 | 2021-03-26 | 常州大学 | Alkaline water-system mixed liquid flow battery based on electroactive phenazine derivative negative electrode |
| CN112563521B (en) * | 2020-12-01 | 2021-12-21 | 常州大学 | Alkaline water-system mixed liquid flow battery based on electroactive phenazine derivative negative electrode |
| CN113121547A (en) * | 2021-04-08 | 2021-07-16 | 常州大学 | Nitrogen-containing polyquinone organic electrode material and preparation method and application thereof |
| CN114883559A (en) * | 2022-04-29 | 2022-08-09 | 安徽大学 | Naphthoquinone-quinoxaline organic electrode material and application thereof in aqueous zinc ion battery |
| CN115057862A (en) * | 2022-04-29 | 2022-09-16 | 安徽大学 | Pyrazine-quinoxaline organic electrode material and application thereof in lithium ion battery |
| CN114883559B (en) * | 2022-04-29 | 2023-08-04 | 安徽大学 | Naphthoquinone-quinoxaline organic electrode material and application thereof in water-based zinc ion battery |
| CN115057862B (en) * | 2022-04-29 | 2023-09-08 | 安徽大学 | Pyrazine-quinoxaline organic electrode material and application thereof in lithium ion battery |
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