Porphyrin two-dimension covalent organic framework conjugated polymer, and preparation method and application thereof

A covalent organic framework, conjugated polymer technology, applied in the field of porphyrin two-dimensional covalent organic framework conjugated polymers, can solve the problems of reduced Coulombic efficiency, poor cycle stability, low theoretical specific capacity, etc., and achieve excellent Effect of rate capability, long cycle life, high specific capacity

Inactive Publication Date: 2016-02-24
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although it has a high theoretical capacity, the inorganic anode material itself has its obvious shortcomings: the volume expansion induced by the lithium intercalation process, and the resulting loss of a large amount of irreversible capacity, the decrease of the first Coulombic efficiency, poor cycle stability, etc.
Graphite (372mAh / g) is a typical traditional carbon-based material as the negative electrode of lithium-ion batteries, but its low theoretical specific capacity is difficult to meet the rapid growth demand of batteries (Tarascon, J.M.; Armand, M., Nature, 414( 6861), 359-367(2001)

Method used

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  • Porphyrin two-dimension covalent organic framework conjugated polymer, and preparation method and application thereof
  • Porphyrin two-dimension covalent organic framework conjugated polymer, and preparation method and application thereof
  • Porphyrin two-dimension covalent organic framework conjugated polymer, and preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0059] The synthesis of embodiment 1, COF-1

[0060] A copper foil with an area of ​​1.5 cm×8 cm was placed in a three-neck flask containing a mixed solution of toluene (15 ml) and triethylamine (15 ml). Copper foil was treated with 0.5M hydrochloric acid solution, secondary water, ethanol, and acetone in sequence before use. After 30 minutes of nitrogen protection, the catalyst bistriphenylphosphine palladium dichloride (8.4mg, 0.012mmol) and cuprous iodide (2.2mg, 0.012mmol) were added to the there-necked flask, and nitrogen protection was carried out at room temperature, and stirred for 1 Hour. Add 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin (1.2mg, 0.0017mmol), 1,4-diiodobenzene (1.1mg, 0.0034mmol), and the reaction system was refluxed under nitrogen protection 48 hours. After the reaction, a dark purple film was formed on the copper sheet, and the copper sheet was washed three times with acetone, methanol, dichloromethane, and diethyl ether to obtain a two-dimensiona...

Embodiment 2

[0066] The synthesis of embodiment 2, COF-2

[0067] A copper foil with an area of ​​1.5cm×8cm was placed in a three-necked bottle filled with a pyridine (30ml) solution. Copper foil was treated with 0.5M hydrochloric acid solution, secondary water, ethanol, and acetone in sequence before use. After nitrogen protection for 30 minutes, 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin (1.2 mg, 0.0017 mmol) was added, and the reaction system was refluxed for 48 hours under nitrogen protection. After the reaction, a purple film was formed on the copper sheet, and the copper sheet was washed three times with acetone and N,N'-dimethylformamide to obtain a two-dimensional covalent organic framework conjugated polymer COF-2 film. Synthesis schematic as Figure 1b shown.

[0068] Scanning electron microscope (SEM) test results ( Figure 2b ) showed that the resulting two-dimensional covalent organic framework conjugated polymer COF-2 film prepared by this method was continuously and u...

Embodiment 3

[0073] The synthesis of embodiment 3, COF-3

[0074] A copper foil with an area of ​​1.5 cm×8 cm was placed in a three-neck flask containing a mixed solution of toluene (15 ml) and triethylamine (15 ml). Copper foil was treated with 0.5M hydrochloric acid solution, secondary water, ethanol, and acetone in sequence before use. After nitrogen protection for 30 minutes, the catalyst bistriphenylphosphine palladium dichloride (8.4mg, 0.012mmol) and cuprous iodide (2.2mg, 0.012mmol) were added to the there-necked flask, and stirred under nitrogen protection at room temperature for 1 hour . After addition of 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin (1.2 mg, 0.0017 mmol), 1,4-diiodo-1,3-butadiyne (1.02 mg, 0.0034 mmol) , the reaction system was refluxed for 48 hours under the protection of nitrogen. After the reaction, a brown-purple film was formed on the copper sheet, and the copper sheet was washed three times with acetone, methanol, dichloromethane, and diethyl ether to o...

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Abstract

The invention belongs to the fields of a metal ion battery and a super capacitor, and concretely relates to a porphyrin two-dimension covalent organic framework conjugated polymer, and a preparation method and an application thereof. A structural formula of the porphyrin two-dimension covalent organic framework conjugated polymer is shown in formula (I), wherein m=0 or 1, n=0 or 1. The porphyrin two-dimension covalent organic framework conjugated polymer can be directly used as a cathode material of the metal ion battery and the super capacitor, so that the cathode material shows excellent properties, which include good cycle performance, high specific capacity and excellent rate capability; the polymer powder also has the same effects and properties, and can be used as a cathode material of other metal ion (sodium, potassium, zinc, nickel, etc.) batteries and super capacitors.

Description

technical field [0001] The invention belongs to the field of metal ion batteries and supercapacitors, and specifically relates to a porphyrin two-dimensional covalent organic framework conjugated polymer, its preparation method and application. Background technique [0002] In recent years, Li-ion batteries have been widely used in portable electronic devices (Kim, YS; Xie, Y.N; Wen, X.N; Wang, S.H; Kim, S.J; Song, HK; Wang, Z.L, NanoEnergy 14, 77–86 (2015 )). Electrode materials with high specific capacity, excellent rate capability, and longer cycle life are crucial determinants for improving battery performance. Inorganic and carbon-based anode materials have attracted extensive attention. TiS since 1976 2 It is used as anode material (Whittingham, M.S. Electrochemicalenergystorageandintercalationchemistry.Science192, 1226–1227 (1976)), various inorganic anode materials with high energy density, such as Si, Co 3 o 4 , Fe 3 o 4 and SnO 2 attracted the attention of ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D519/00C07D487/22H01G11/48H01M4/62
CPCC07D487/22C07D519/00H01G11/48H01M4/624Y02E60/10Y02E60/13
Inventor 刘辉彪李玉良李勇军杨慧
Owner INST OF CHEM CHINESE ACAD OF SCI
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