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Method for synthesizing porphyrin-based two-dimensional metal organic framework nanosheet array on zinc substrate and battery

A metal-organic framework and nanosheet array technology, which is applied in the field of electrochemical power supply, can solve the problems such as the inability to adjust the wall thickness and sheet size of MOF, the incompact deposition of zinc metal, and the inapplicability to the battery field, so as to ensure ion transport, The synthesis method is simple, and the preparation process is green and pollution-free

Active Publication Date: 2022-07-12
TIANJIN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, Zn metal is usually not densely deposited in open channels forming a large surface area, which leads to more side reactions between the deposited Zn and the aqueous electrolyte.
[0005] The preparation method of metal-organic framework nanoarrays has been reported before, mainly using iron, cobalt or nickel as the substrate, and the wall thickness and sheet size of the prepared MOF cannot be adjusted (Nano Energy 44 (2018) 345–352 and NanoEnergy 62 ( 2019) 876–882), so it is not suitable for the battery field; in addition, MOF arrays grown on copper current collectors have also been reported, but such current collectors need to pre-deposit metal active materials before they can be used (such as the article EnergyStorage Materials 11 ( 2018) 267–273 and Advanced Functional Materials 2021, 2101034), these methods have complicated steps and harsh application conditions

Method used

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  • Method for synthesizing porphyrin-based two-dimensional metal organic framework nanosheet array on zinc substrate and battery
  • Method for synthesizing porphyrin-based two-dimensional metal organic framework nanosheet array on zinc substrate and battery
  • Method for synthesizing porphyrin-based two-dimensional metal organic framework nanosheet array on zinc substrate and battery

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Experimental program
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Effect test

Embodiment 1

[0040] (1) Preparation of porphyrin-based Zn-TCPP nanosheet arrays.

[0041] A method for synthesizing a porphyrin-based two-dimensional metal-organic framework (MOF) nanosheet array on a zinc substrate, characterized in that the preparation process at least comprises the following steps:

[0042] The first step is to prepare the solution: at room temperature, weigh a certain amount of 4,4,4,4-(porphyrin-5,10,15,20-tetraformyl)tetrakis(benzoic acid) (TCPP) and dissolve it in In dimethylformamide / ethanol mixed solvent, ultrasonically dispersed, the concentration is 2 mgml -1 , to obtain the precursor solution.

[0043] The second step is to polish the zinc sheet with 600-1000 mesh sandpaper to remove the oxide layer on the surface;

[0044] In the third step, the precursor solution and the polished zinc substrate are put into a reaction kettle for reaction at a reaction temperature of 60°C and a time of 5 minutes to obtain a two-dimensional Zn-TCPP array;

[0045] In the fou...

Embodiment 2

[0051] The difference from implementation 1 is that the mixed solvent in the first step is a mixture of dimethylformamide and methanol, the solvent in the third step is water, and the reaction time in the third step is 10 minutes. The height of the grown two-dimensional Zn-TCPP array was extended to about 1 μm, no dendrites were generated in the zinc deposition test, and the deposition method was U-shaped.

[0052] The rest are the same as in Embodiment 1, and are not repeated here.

Embodiment 3

[0054] The difference from implementation 1 is that the mixed solvent of the first step is a mixture of ethanol and dimethyl sulfoxide, the solvent of the third step is methanol, the reaction time of the third step is 30 minutes, and the grown two-dimensional Zn-TCPP array is highly Extending to about 1.5 μm, the thickness of the Zn-TCPP sheet is nearly 100 nm. No dendrites were produced in the zinc deposition test, and the deposition pattern was U-shaped.

[0055] The rest are the same as in Embodiment 1, and are not repeated here.

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Abstract

The invention belongs to the technical field of electrochemical power supplies, and particularly relates to a method for synthesizing a porphyrin-based two-dimensional metal organic framework (MOF) nanosheet array on a zinc substrate, which at least comprises the following steps: 1, preparing a solution: dispersing a precursor of a porphyrin structure containing carboxyl in a mixed solvent to obtain a precursor solution; 2, the precursor solution and a zinc substrate are subjected to a reaction, and a porphyrin-based two-dimensional Zn-MOF array is obtained; and step 3, washing the porphyrin-based two-dimensional Zn-MOF array obtained in the step 2 with a solvent, and then removing the solvent, so that the porphyrin-based two-dimensional MOF nanosheet array is attached to the zinc substrate. The MOF open-pore array structure is efficiently synthesized through a surfactant-free substrate induction method, and the MOF open-pore array structure is used for the negative electrode of the metal ion battery, so that U-shaped deposition of metal can be induced, generation of dendritic crystals can be inhibited, and the cycle performance of the metal ion battery is improved. Meanwhile, the MOF nano array is simple to synthesize and suitable for large-scale production.

Description

technical field [0001] The invention belongs to the technical field of electrochemical power supply, and in particular relates to a method for synthesizing a porphyrin-based two-dimensional metal-organic framework (MOF) nanosheet array on a zinc substrate. The nanosheet array prepared by the method can protect a metal negative electrode. Background technique [0002] The burning of traditional fossil fuels not only reduces energy reserves, but also brings serious environmental pollution problems. With the depletion of the earth's resources and the aggravation of environmental pollution, the pursuit of clean energy has received more and more attention. [0003] Take the aqueous zinc battery as an example, because of its high theoretical volume capacity (5855 mAh cm -3 ), low redox potential (-0.762 V vs SHE), and environmental friendliness. However, Zn dendrite growth, interfacial corrosion, and side reactions at the anode-electrolyte interface (such as hydrogen evolution r...

Claims

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Application Information

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IPC IPC(8): H01M4/04B82Y40/00C08G83/00
CPCH01M4/0404H01M4/045C08G83/008B82Y40/00Y02E60/10
Inventor 杨全红王飞飞杨春鹏
Owner TIANJIN UNIV
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