Porphyrin polymer and preparation method and application thereof in positive electrode material

Abstract

The invention discloses a porphyrin polymer as well as a preparation method and application thereof in a positive electrode material. The porphyrin polymer is obtained by polymerizing two active sites, and a polymerization monomer has the characteristics of good conductivity, good thermal stability, common and easily available materials, purifying by recrystallization, low production cost and thelike. Through the strategy of polymerization and introduction of a carbon-carbon triple bond group into a molecule, the prepared organic positive electrode material solves the problems that monomer small molecules are easy to dissolve in an organic solvent, the electronic conductivity is low and the like. When the polymer is applied to an alkali metal ion battery or an alkaline earth metal ion battery, the result shows that the obtained battery has good specific discharge capacity and cycling stability, the electrochemical performance of the battery can be remarkably improved after polymerization, and the polymer has potential practical application value in the field of electrochemical energy storage.

Description

technical field

[0001] The invention relates to a preparation method of positive electrode materials, in particular to a porphyrin polymer, its preparation method and its application in positive electrode materials. Background technique

[0002] The development of modern civilization has brought many conveniences to human's daily life, but a series of energy problems have also followed. How to develop new power batteries and sustainable development of new energy and efficient energy storage systems is particularly important. With the rapid development of electric vehicles and large-scale electrochemical energy storage devices, it is necessary to explore energy storage materials with high energy density, low cost, and safety and reliability. Lithium-ion batteries have played an important role in powering mobile phones, hybrid vehicles, and laptops due to their high energy density, high power density, long life, and environmental protection. Since lithium-ion batteries were c...

Examples

Embodiment 1

[0037] 1, a kind of porphyrin polymer, its preparation process is as follows:

[0038]

[0039] (1) chemical structural formula is the synthesis of the intermediate of a:

[0040]2,6-bis-octyloxybenzaldehyde (3.772g, 10.40mmol) and dipyrromethane (1.52g, 10.41mmol) were added to a 1000mL three-necked round-bottomed flask, 500mL of dichloromethane was added as a solvent, and Under argon protection, stir at room temperature for 10 minutes, then add trifluoroacetic acid (0.418mL, 9.5mmol), stir the mixture at room temperature for 4 hours, then add dichlorodicyanobenzoquinone (2.36g, 10.4mmol), After stirring for another 1 h, the reaction was quenched by the addition of 5 mL of triethylamine, followed by purification by chromatography using a 1:1 volume ratio of dichloromethane to petroleum ether as an eluent to give 10,20-bis(2,6-bisoctyloxy base) porphyrin (760 mg, 15%).

[0041] (2) chemical structural formula is the synthesis of the intermediate of b:

[0042] 10,20-bis(...

Embodiment 2

[0052] The porphyrin polymer prepared in Example 1 is assembled into a button battery as the positive electrode active material of a lithium ion battery, and the specific method is as follows:

[0053] Dissolve 10 parts of porphyrin polymer, 8 parts of conductive agent acetylene black, and 2 parts of binder polyvinylidene fluoride in N-methylpyrrolidone (10 mg / ml) in a weight ratio, grind thoroughly, and grind evenly The slurry is coated on a stainless steel sheet, and the solvent is dried in a vacuum oven at 80°C to be used as the positive electrode of the battery, the metal lithium sheet is used as the negative electrode, and the electrolyte is 1mol / L LiPF 6 , the solvent molecule is PC / EC / DMC (v / v / v=1:1:3), assembled into a button battery under an argon atmosphere, and electrochemically performed in the range of 4.5-1.8V with a constant current charge and discharge instrument Performance Testing.

Embodiment 3

[0055] The intermediate product e obtained in step (5) of Example 1, namely 5,15-diynyl-10,20-bis(2,6-bisoctyloxy)porphyrin zinc monomer, was used as the positive electrode active material for lithium ion batteries Assembled into a button battery, the specific method is as follows:

[0056] 10 parts by weight of 5,15-diacetylenyl-10,20-bis(2,6-bisoctyloxy)porphyrin zinc and 8 parts of conductive agent acetylene black, 2 parts of binder polyylidene fluoride Ethylene is dissolved in N-methylpyrrolidone (10mg / ml), fully ground, and the evenly ground slurry is coated on a stainless steel sheet, and the solvent is dried in a vacuum oven at 80°C and used as the positive electrode of the battery, and the metal lithium sheet is used as the negative electrode , the electrolyte is 1mol / L LiPF 6 , the solvent molecule is PC / EC / DMC (v / v / v=1:1:3), assembled into a button battery under an argon atmosphere, and electrochemically performed in the range of 4.5-1.8V with a constant current cha...

technical field

[0001] The invention relates to a preparation method of positive electrode materials, in particular to a porphyrin polymer, its preparation method and its application in positive electrode materials. Background technique

[0002] The development of modern civilization has brought many conveniences to human's daily life, but a series of energy problems have also followed. How to develop new power batteries and sustainable development of new energy and efficient energy storage systems is particularly important. With the rapid development of electric vehicles and large-scale electrochemical energy storage devices, it is necessary to explore energy storage materials with high energy density, low cost, and safety and reliability. Lithium-ion batteries have played an important role in powering mobile phones, hybrid vehicles, and laptops due to their high energy density, high power density, long life, and environmental protection. Since lithium-ion batteries were c...

Examples

Embodiment 1

[0037] 1, a kind of porphyrin polymer, its preparation process is as follows:

[0038]

[0039] (1) chemical structural formula is the synthesis of the intermediate of a:

[0040]2,6-bis-octyloxybenzaldehyde (3.772g, 10.40mmol) and dipyrromethane (1.52g, 10.41mmol) were added to a 1000mL three-necked round-bottomed flask, 500mL of dichloromethane was added as a solvent, and Under argon protection, stir at room temperature for 10 minutes, then add trifluoroacetic acid (0.418mL, 9.5mmol), stir the mixture at room temperature for 4 hours, then add dichlorodicyanobenzoquinone (2.36g, 10.4mmol), After stirring for another 1 h, the reaction was quenched by the addition of 5 mL of triethylamine, followed by purification by chromatography using a 1:1 volume ratio of dichloromethane to petroleum ether as an eluent to give 10,20-bis(2,6-bisoctyloxy base) porphyrin (760 mg, 15%).

[0041] (2) chemical structural formula is the synthesis of the intermediate of b:

[0042] 10,20-bis(...

Embodiment 2

[0052] The porphyrin polymer prepared in Example 1 is assembled into a button battery as the positive electrode active material of a lithium ion battery, and the specific method is as follows:

[0053] Dissolve 10 parts of porphyrin polymer, 8 parts of conductive agent acetylene black, and 2 parts of binder polyvinylidene fluoride in N-methylpyrrolidone (10 mg / ml) in a weight ratio, grind thoroughly, and grind evenly The slurry is coated on a stainless steel sheet, and the solvent is dried in a vacuum oven at 80°C to be used as the positive electrode of the battery, the metal lithium sheet is used as the negative electrode, and the electrolyte is 1mol / L LiPF 6 , the solvent molecule is PC / EC / DMC (v / v / v=1:1:3), assembled into a button battery under an argon atmosphere, and electrochemically performed in the range of 4.5-1.8V with a constant current charge and discharge instrument Performance Testing.

Embodiment 3

[0055] The intermediate product e obtained in step (5) of Example 1, namely 5,15-diynyl-10,20-bis(2,6-bisoctyloxy)porphyrin zinc monomer, was used as the positive electrode active material for lithium ion batteries Assembled into a button battery, the specific method is as follows:

[0056] 10 parts by weight of 5,15-diacetylenyl-10,20-bis(2,6-bisoctyloxy)porphyrin zinc and 8 parts of conductive agent acetylene black, 2 parts of binder polyylidene fluoride Ethylene is dissolved in N-methylpyrrolidone (10mg / ml), fully ground, and the evenly ground slurry is coated on a stainless steel sheet, and the solvent is dried in a vacuum oven at 80°C and used as the positive electrode of the battery, and the metal lithium sheet is used as the negative electrode , the electrolyte is 1mol / L LiPF 6 , the solvent molecule is PC / EC / DMC (v / v / v=1:1:3), assembled into a button battery under an argon atmosphere, and electrochemically performed in the range of 4.5-1.8V with a constant current cha...

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