Two-dimensional covalent organic framework materials based on phenoxazine and their preparation methods and applications

A technology of covalent organic framework and phenoxazine, which is applied in secondary batteries, final product manufacturing, electrolyte storage battery manufacturing, etc., can solve problems such as slow redox kinetics, low active site utilization, poor cycle stability, etc. , to achieve fast redox kinetics, good application prospects, and high crystallinity

Active Publication Date: 2022-07-19
NANJING TECH UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, most of the current COFs powders directly applied to electrode materials exhibit poor cycling stability, rather low active site utilization, and slow redox kinetics due to their low electrical conductivity, requiring the development of complex strategies (such as introducing conductive guests) to overcome this problem
Furthermore, it is known that the redox potential of COFs rarely exceeds 3 V vs. Li / Li + , thus forming a low-voltage battery, which greatly limits its application

Method used

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  • Two-dimensional covalent organic framework materials based on phenoxazine and their preparation methods and applications
  • Two-dimensional covalent organic framework materials based on phenoxazine and their preparation methods and applications
  • Two-dimensional covalent organic framework materials based on phenoxazine and their preparation methods and applications

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preparation example Construction

[0036] Another aspect of the embodiments of the present invention also provides a method for preparing a phenoxazine-based two-dimensional covalent organic framework material, comprising:

[0037] Under a protective atmosphere, a uniformly mixed reaction system containing 10-methylphenoxazine-2,7-diamine, aryl aldehydes, aqueous acetic acid and solvent was reacted at 100-150 °C for 3-7 days to prepare Two-dimensional covalent organic framework materials based on phenoxazine were obtained.

[0038] In some specific embodiments, the aryl aldehydes include 1,3,5-benzenetricarbaldehyde (TFB), 2,4,6-trimethoxybenzene-1,3,5-tricarbaldehyde ( Any one of TpOMe) and 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde (Tp).

[0039] Further, the concentration of the acetic acid aqueous solution is 3-9 mol / L.

[0040] Further, the solvent is a high boiling point solvent with a boiling point range of 80-180°C.

[0041] Further, the solvent includes any one or a combination of two or more of ...

Embodiment 1

[0067] Preparation of phenoxazine-based two-dimensional covalent organic framework material DAPO-TFB-COF:

[0068] Add 102.1mg 10-methylphenoxazine-2,7-diamine and 48.6mg 1,3,5-benzenetricarboxaldehyde to a 10mL Slack tube, then add 2mL acetonitrile, and after ultrasonic dissolving, add 0.6mL with a concentration of 3 mol / L acetic acid aqueous solution, then the reaction system was degassed in liquid nitrogen by three cycles of freezing-vacuum-thawing cycles, and the reaction mixture was sealed in a constant temperature oil bath, heated to 120°C, and kept for 3 days. After the reaction was completed, it was cooled to room temperature, and the obtained mixture was centrifuged to collect the solid, then centrifuged and washed with N,N-dimethylformamide and tetrahydrofuran, and vacuum-dried at 80 °C for 12 h to obtain a reddish-brown powder DAPO-TFB-COF. The yield was DAPO-TFB-COF. is 98%.

Embodiment 2

[0070] Preparation of phenoxazine-based two-dimensional covalent organic framework material DAPO-TFB-COF:

[0071] Add 102.1 mg of 10-methylphenoxazine-2,7-diamine and 48.6 mg of 1,3,5-benzenetricarboxaldehyde to a 10 mL Slack tube, then add 2 mL of dioxane, dissolve by ultrasonic and add 0.6 Aqueous acetic acid with a concentration of 6 mol / L in mL. The reaction system was then degassed in liquid nitrogen in three cycles of freeze-vacuum-thaw cycles. The reaction mixture was sealed in a constant temperature oil bath, heated to 120° C. and kept for 3 days. After the reaction was completed, it was cooled to room temperature. The obtained mixture was centrifuged to collect solids, and then washed with N,N-dimethylformamide and tetrahydrofuran by centrifugation. Vacuum drying at 80°C for 12h gave DAPO-TFB-COF as a reddish-brown powder with a yield of 98%.

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Abstract

The invention discloses a phenoxazine-based two-dimensional covalent organic framework material and a preparation method and application thereof. The phenoxazine-based two-dimensional covalent organic framework material has a structure as shown in any one of formula (I), formula (II) or formula (III): the phenoxazine-based two-dimensional The covalent organic framework material has high crystallinity and specific surface area, uniform pore size distribution and good thermal stability, and the phenoxazine-based two-dimensional covalent organic framework material has a high redox potential (~3.5V). vs. Li / Li + ) and fast redox kinetics, therefore, the phenoxazine-based two-dimensional covalent organic framework materials prepared in the present invention can be applied to cathode materials for lithium ion batteries, and have good application prospects in the field of functional organic materials.

Description

technical field [0001] The invention belongs to the field of organic functional materials, and in particular relates to a two-dimensional covalent organic framework material based on phenoxazine and a preparation method and application thereof. Background technique [0002] As a rechargeable and dischargeable secondary battery, lithium-ion batteries have been successfully used in various energy storage fields since they were developed because of their high energy and power density and long service life. The cathode material is an important factor restricting the improvement of battery energy density. Compared with traditional cathode materials (transition metal oxides), organic cathode materials (including carbonyl compounds, conductive polymers, radical compounds, etc.) have been widely used in lithium due to their easy availability of raw materials, diverse structures, and environmental friendliness. Ion battery cathode material. However, the existing organic materials a...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G73/06H01M4/137H01M4/60H01M10/0525H01M10/058
CPCC08G73/06H01M4/608H01M10/0525H01M10/058H01M4/137Y02E60/10Y02P70/50
Inventor 杜亚杨海申孟智颖张赢董梦青崔超慧
Owner NANJING TECH UNIV
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