CN114744143A - Method for synthesizing porphyrin-based two-dimensional metal organic framework nanosheet array on zinc substrate and battery - Google Patents

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

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CN114744143A
CN114744143A CN202210512324.8A CN202210512324A CN114744143A CN 114744143 A CN114744143 A CN 114744143A CN 202210512324 A CN202210512324 A CN 202210512324A CN 114744143 A CN114744143 A CN 114744143A
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porphyrin
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CN114744143B (en
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杨全红
王飞飞
杨春鹏
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Tianjin University
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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: step one, preparing a solution: dispersing a precursor of a porphyrin structure containing carboxyl in a mixed solvent to obtain a precursor solution; secondly, reacting the precursor solution with a zinc substrate to obtain a porphyrin-based two-dimensional Zn-MOF array; and thirdly, washing the porphyrin-based two-dimensional Zn-MOF array obtained in the second step by using a solvent, and then removing the solvent, so that the porphyrin-based two-dimensional MOF nanosheet array is attached to the zinc substrate. According to the invention, the MOF open pore array structure is efficiently synthesized by a surfactant-free substrate induction method, and when the MOF open pore array structure is used for a metal ion battery negative electrode, U-shaped deposition of metal can be induced, and generation of dendritic crystals is inhibited, so that 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

Method for synthesizing porphyrin-based two-dimensional metal organic framework nanosheet array on zinc substrate and battery
Technical Field
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.
Background
The combustion of traditional fossil fuels not only reduces energy reserves, but also brings about serious environmental pollution problems. With the exhaustion of earth resources and the aggravation of environmental pollution problems, the search for clean energy is receiving more and more extensive attention.
An aqueous zinc cell is exemplified by its relatively high theoretical volume capacity (5855 mAh cm)-3) Low redox potential (-0.762V vs SHE) and environmental friendliness. However, zinc dendrite growth, interfacial corrosion, and side reactions at the anode-electrolyte interface (such as hydrogen evolution reaction, HER), etc., have severely hindered the use of zinc batteries.
Recently, methods of interfacial modification by using various coatings, such as organic polymers, inorganic compounds and organic-inorganic hybrids, have been widely used to regulate the diffusion, nucleation and deposition of Zn ions to achieve reversible plating/stripping and to prevent zinc dendrites. However, a large volume change of the zinc negative electrode during the plating/stripping process will inevitably lead to detachment or cracking of the plating layer. It has been demonstrated that constructing a 3D matrix with open channels for Zn metal anodes can effectively mitigate volume changes. However, zinc metal is generally not deposited densely in open channels forming a large surface area, which results in more side reactions between the deposited zinc and the aqueous electrolyte.
The preparation method of the metal organic framework Nano array has been reported before, mainly takes iron, cobalt or nickel as a substrate, and the wall thickness and the sheet size of the prepared MOF cannot be adjusted (Nano Energy 44 (2018) 345-; furthermore, MOF arrays grown on copper current collectors have been reported, however, such current collectors require a prior deposition of metal active substances before they can be used (e.g. the articles Energy Storage Materials 11 (2018) 267 Materials 273 and Advanced Functional Materials 2021, 2101034), and these methods are complicated in steps and harsh in application conditions.
In view of the above, the present invention aims to provide a method for synthesizing a porphyrin-based two-dimensional Metal Organic Framework (MOF) nanosheet array on a zinc substrate, which can induce lateral Zn deposition on MOF sheets to balance surface Zn deposition, referred to as U-shaped Zn deposition for short, to eliminate "tip effect" and achieve uniform Zn deposition. The two-dimensional MOF nano array has enough zinc-philic sites and open ion channels, can preferentially adsorb and nucleate Zn ions on the MOF sheet, can promote the transverse Zn deposition on the MOF sheet, realizes the spatial controllable U-shaped zinc plating, and further inhibits the generation of zinc dendrites.
Disclosure of Invention
The invention aims to: in response to the deficiencies of the prior art, a method is provided for synthesizing an array of porphyrin-based two-dimensional Metal Organic Framework (MOF) nanoplates on a zinc substrate that can induce lateral Zn deposition on MOF sheets to balance surface Zn deposition, referred to as U-shaped Zn deposition, to eliminate the "tip effect" and achieve uniform Zn deposition. The two-dimensional MOF nano array has enough zinc-philic sites and open ion channels, can preferentially adsorb and nucleate Zn ions on the MOF sheet, can promote the transverse Zn deposition on the MOF sheet, realizes the spatial controllable U-shaped zinc plating, and further inhibits the generation of zinc dendrites.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of synthesizing a porphyrin-based two-dimensional metal-organic framework nanosheet array on a zinc substrate, comprising at least the steps of:
step one, preparing a solution: dispersing a precursor of a porphyrin structure containing carboxyl in a mixed solvent to obtain a precursor solution;
secondly, reacting the precursor solution with a zinc substrate to obtain a porphyrin-based two-dimensional Zn-MOF array;
and thirdly, washing the porphyrin-based two-dimensional Zn-MOF array obtained in the second step by using a solvent, and then removing the solvent, so that the porphyrin-based two-dimensional MOF nanosheet array is attached to the zinc substrate, and unreacted ligands can be washed away by using ethanol. The specific working principle is as follows: in the reaction process, the precursor of the porphyrin structure containing the carboxyl tends to be vertically adsorbed on the surface of the zinc foil, which is related to the interaction between saddle-shaped nodes and conjugated pi bonds of porphyrin ligands and the surface of the zinc foil with negative charges, the surface of the zinc foil is oxidized by the precursor of the porphyrin structure containing the carboxyl to generate zinc ions, and the zinc ions are immediately coordinated with the precursor of the porphyrin structure containing the carboxyl and assembled on active sites on the surface of the zinc foil. Then, the excessive precursor molecules of porphyrin structures containing carboxyl continue to react with the dissolved Zn ions to form Zn-MOF nano arrays vertical to the metal zinc foil.
As an improvement of the method for synthesizing a porphyrin-based two-dimensional metal organic framework nanosheet array on a zinc substrate, the porphyrin-based two-dimensional MOF nanosheet array has an adjustable open pore structure, and the adjustment is realized through the distance between the nanosheets; and the nano-sheets in the porphyrin-based two-dimensional MOF nano-sheet array are perpendicular to the zinc substrate, and the porphyrin-based two-dimensional MOF nano-sheet array has abundant channels (channels formed by open pore structures) for transmitting ions. Meanwhile, the MOF wall has higher metal ion affinity, and is beneficial to the adsorption of metal ions.
As an improvement of the method for synthesizing the porphyrin-based two-dimensional metal organic framework nanosheet array on the zinc substrate, the metal center in the porphyrin-based two-dimensional MOF nanosheet array can be expanded to zinc.
As an improvement of the method for synthesizing the porphyrin-based two-dimensional metal organic framework nanosheet array on the zinc substrate, the pore diameter of the open pore structure of the porphyrin-based two-dimensional MOF nanosheet array is 10 nm-2 μm.
As an improvement of the method for synthesizing the porphyrin-based two-dimensional metal organic framework nanosheet array on the zinc substrate, in the second step, the reaction temperature range is 25-180 DEG CoAnd C, the reaction time is 1min-24 h. Preferably 5 minutes to 1 hour, more preferably 5 minutes to 20 minutes.
As an improvement of the method for synthesizing the porphyrin-based two-dimensional metal organic framework nanosheet array on the zinc substrate, in the first step, the mixed solvent is at least two of dimethylformamide, ethanol, methanol, ethylene glycol, methyl pyrrolidone and dimethyl sulfoxide. And the solvent in the third step is at least one of ethanol, water, methanol and petroleum ether.
As an improvement of the method for synthesizing the porphyrin-based two-dimensional metal organic framework nanosheet array on the zinc substrate, the precursor of the porphyrin structure containing carboxyl is 4,4,4,4- (porphyrin-5, 10,15, 20-tetracarboxyl) tetra (benzoic acid), and the concentration of the precursor solution is 1-1000 mg ml-1Preferably 2-5 mg ml-1。
As an improvement of the method for synthesizing the porphyrin-based two-dimensional metal organic framework nanosheet array on the zinc substrate, the zinc substrate is polished before the second step. To remove oil stains or zinc oxide layers on the surface.
Compared with the prior art, the material disclosed by the invention solves the stacking problem of the MOF in the porphyrin-based two-dimensional MOF material, optimizes a synthesis method and ensures the ion transport property of the MOF material. The material has the advantages of novel structure, simple synthesis method, low cost, suitability for industrialization and the like. The porphyrin-based two-dimensional metal-philic MOF array is used for a metal negative electrode, can realize U-shaped deposition of zinc, prevents generation of metal dendrites, and enables the metal negative electrode to have excellent cycle performance and rate capability. The principle is as follows: the MOF sheets containing N and O sites are zinc-philic and can pre-adsorb Zn ions uniformly and then plate upward from the anode surface, depositing Zn laterally on these sheets, eventually achieving a dynamically balanced U-shaped deposition of the bottom and sides. The synthesized Zn-MOF array attached zinc metal cathode can induce the U-shaped deposition of zinc to realize longer battery cycle. The full battery assembled by the zinc metal cathode attached to the synthesized MOF array and the vanadium-based anode has excellent cycling stability. The full battery assembled by the zinc cathode attached to the synthesized MOF array and the vanadium-based, manganese-based or Prussian blue cathode has excellent cycling stability.
In the second step, no surfactant is used for regulating and controlling the MOF interlamellar spacing, so that the surfactant is prevented from polluting the MOF array, and further the function of the MOF array is prevented from being influenced.
Compared with the prior art, the method has the following advantages:
firstly, the method is mild in condition, simple to operate and green and pollution-free in preparation process, and the nano-sheet array is synthesized by utilizing the reaction between metal zinc and carboxyl in a porphyrin precursor.
Second, the method can enable controlled adjustment of MOF nanosheet array height and thickness.
Thirdly, effective synthesis of the MOF nanosheet array can still be achieved by replacing different zinc substrates.
Fourth, the synthesized zinc metal negative electrode attached by the Zn-MOF array can induce the U-shaped deposition of zinc to realize longer cycle stability.
The invention also provides a battery, which comprises a positive electrode, a negative electrode, electrolyte and a separation film, and is characterized in that: the negative electrode is a zinc-based porphyrin-based two-dimensional MOF nanosheet array prepared by the method. The negative electrode can induce the U-shaped deposition of zinc and has the function of inhibiting dendritic crystals.
The positive electrode is a vanadium-based positive electrode, a manganese-based positive electrode or Prussian blue. Wherein the vanadium-based positive electrode is at least one of vanadium oxide, zinc vanadate, ammonium vanadate and the like. The manganese-based positive electrode is manganese dioxide.
The solute of the electrolyte comprises at least one of zinc sulfate and zinc trifluoromethanesulfonate, and the solvent comprises deionized water, ethanol or ethylene glycol.
The isolating membrane is one of glass fiber membranes (GF-A, B, C and D) and cellulose membranes.
The battery has the characteristics of high safety and long service life, and has excellent cycle stability.
Compared with the prior art, the invention provides a method for synthesizing a porphyrin-based two-dimensional MOF nanosheet array for a metal ion battery, further optimizes the method for synthesizing the porphyrin-based two-dimensional MOF nanosheet array, realizes the synthesis of the efficient and green porphyrin-based two-dimensional MOF nanosheet array, and provides a new idea for promoting the development of a metal ion battery cathode. According to the invention, by developing the two-dimensional MOF nanosheet array growing on the surface of the zinc cathode in situ, the 'tip effect' in the electroplating process is hopefully relieved, and the non-compact deposition of the Zn anode can be relieved. Furthermore, zinc-philic matrices with nano-array structures and open channels are particularly promising for lateral zinc deposition, preventing zinc dendrite growth.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the two-dimensional Zn-TCPP array obtained in example 1.
FIG. 2 is a Transmission Electron Microscopy (TEM) image of the two-dimensional Zn-TCPP array obtained in example 1.
Fig. 3 is a graph of cycle performance of the battery in the example.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore not limited to the specific embodiments disclosed below.
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Example 1
Preparing a porphyrin-based Zn-TCPP nanosheet array.
A method for synthesizing a porphyrin-based two-dimensional Metal Organic Framework (MOF) nanosheet array on a zinc substrate, wherein the preparation process comprises at least the following steps:
step one, preparing a solution: weighing a certain amount of 4,4,4,4- (porphyrin-5, 10,15, 20-tetracarboxyl) tetra (benzoic acid) (TCPP) at normal temperature, dissolving in a mixed solvent of dimethyl formamide and ethanol, and ultrasonically dispersing to obtain a solution with a concentration of 2 mg ml-1And obtaining a precursor solution.
Secondly, polishing the zinc sheet by using 600-1000-mesh sand paper to remove an oxide layer on the surface;
thirdly, putting the precursor solution and the ground zinc base into a reaction kettle for reaction at the temperature of 60 ℃ for 5 minutes to obtain a two-dimensional Zn-TCPP array;
and fourthly, washing the two-dimensional Zn-TCPP array obtained in the third step with ethanol, and then removing the ethanol, wherein the ethanol is removed by drying at normal temperature for 3 hours, so as to obtain the perforated material attached with the two-dimensional Zn-TCPP nanosheet array, and an SEM image of the perforated material is shown in figure 1, and a TEM image of the perforated material is shown in figure 2.
As can be seen from fig. 1 and 2: the Zn-TCPP nano sheet array is of a layered structure and has a larger boundary size, and the two-dimensional Zn-TCPP nano sheet array has an open pore structure. The thickness of the Zn-TCPP nano-sheet is 20 nm, and the pore diameter is about 1 μm.
And (II) assembling the synthesized Zn-TCPP/Zn cathode material and zinc vanadate into a zinc ion battery. For zinc symmetric cells, two identical sheets of Zn-TCPP/Zn (d =10 mm, thickness 300 μm) were used as positive and negative electrodes. Using glass fiber (GF-A) as a membrane, 2M ZnSO4The aqueous solution is used as an electrolyte. For the full cell, a mixture of zinc vanadate powder, conductive carbon black and PVDF was mixed in a certain ratio and then dropped on a titanium foil having a thickness of 10 μm to be used as a positive electrode.
And (III) performing electrochemical test on the metal zinc battery.
And (5) carrying out constant-current charge and discharge test on the battery by using a Xinwei battery test system. At 0.5 mA cm-2The cycling stability test was performed at current density. LSV, EIS and CV tests were performed on the workstation. In the HER test, LSV was 1.0M Na2SO4The test was carried out in aqueous solution at a scan rate of 5 mV s-1. The frequency range of the EIS test is from 0.01 Hz to 100 kHz, and the obtained cycle performance graph is shown in FIG. 3, and can be seen from FIG. 3: the Zn-TCPP modified zinc cathode has better cycling stability.
Example 2
The difference from example 1 is that the mixed solvent of dimethylformamide and methanol was used as the first step, water was used as the third step, and the reaction time was 10 minutes. The height of the grown two-dimensional Zn-TCPP array is prolonged to about 1 mu m, no dendritic crystal is generated in a zinc deposition test, and the deposition mode is U-shaped.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The difference from the embodiment 1 is that the first step mixed solvent is a mixture of ethanol and dimethyl sulfoxide, the third step solvent is methanol, the third step reaction time is 30 minutes, the height of the grown two-dimensional Zn-TCPP array is prolonged to about 1.5 mu m, and the thickness of the Zn-TCPP sheet is close to 100 nm. No dendrite is generated in the zinc deposition test, and the deposition mode is U-shaped.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is that the precursor concentration is 4 mg ml-1. The first step of mixed solvent is the mixture of glycol and dimethyl sulfoxide, and the third step of solvent is petroleum ether. No dendrite is generated in the zinc deposition test, and the deposition mode is U-shaped.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from the example 1 is that the mixed solvent in the first step is a mixture of methyl pyrrolidone and dimethyl sulfoxide, and the solvent in the third step is ethanol. The reaction temperature is 25 ℃, the zinc metal surface gradually changes color, and the Zn-TCPP nanosheet array is generated.
No dendrite is generated in the zinc deposition test, and the deposition mode is U-shaped.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from the example 1 is that the mixed solvent of ethanol and methyl pyrrolidone is used as the first step, and water is used as the third step. The reaction temperature is 100 ℃, the reaction time is 10min, and the Zn-TCPP nano-sheet array is generated. No dendrite is generated in the zinc deposition test, and the deposition mode is U-shaped.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from example 1 is that the mixed solvent in the first step is a mixture of methylpyrrolidone and dimethylsulfoxide, and the solvent in the third step is methanol. The reaction temperature is 120 ℃, the reaction time is 1h, and the Zn-TCPP nano-sheet array is generated. No dendrite is generated in the zinc deposition test, and the deposition mode is U-shaped.
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from example 1 is that the precursor concentration is 20 mg ml-1. The mixed solvent in the first step is a mixture of dimethyl formamide and dimethyl sulfoxide, and the solvent in the third step is petroleum ether. No dendrite is generated in the zinc deposition test, and the deposition mode is U-shaped.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from example 1 is that the precursor concentration is 100 mg ml-1. The first step mixed solvent is a mixture of ethylene glycol and methyl pyrrolidone, and the third step solvent is a mixture of ethanol and water. No dendrite is generated in the zinc deposition test, and the deposition mode is U-shaped.
The rest is the same as embodiment 1, and the description is omitted here.
Example 10
The first step mixed solvent is a mixture of dimethyl formamide and dimethyl sulfoxide, and the third step solvent is ethanol. The drying duration of the ethanol removal is 4h, no dendritic crystal is generated in the zinc deposition test, and the deposition mode is U-shaped.
The rest is the same as embodiment 1, and the description is omitted here.
Example 11
This example provides a battery, which includes a positive electrode, a negative electrode, an electrolyte, and a separator, where the positive electrode is vanadium oxide, the negative electrode is the Zn-TCPP modified zinc negative electrode of example 1, the electrolyte is an aqueous solution of zinc sulfate, and the separator is a glass fiber separator, and cycle tests show that the battery has good cycle performance. After disassembling the cell, it was found that dendrites were not found in the negative electrode.
Example 12
This example provides a battery including a positive electrode, a negative electrode, an electrolyte, and a separator, where the positive electrode is zinc vanadate, the negative electrode is the Zn-TCPP modified zinc negative electrode of example 2, the electrolyte is an aqueous solution of zinc sulfate, and the separator is a cellulose separator, which was found to have good cycle performance through cycle testing. After disassembling the cell, it was found that dendrites were not found in the negative electrode.
Example 13
This example provides a battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator, wherein the positive electrode is prussian blue, the negative electrode is the Zn-TCPP modified zinc negative electrode of example 3, the electrolyte is an aqueous solution of zinc sulfate, and the separator is glass fiber GF-D, which was found to have good cycling performance by cycling tests. After disassembling the cell, it was found that dendrites were not found in the negative electrode.
Example 14
This example provides a battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator, wherein the positive electrode is manganese dioxide, the negative electrode is the Zn-TCPP modified zinc negative electrode of example 4, the electrolyte is an aqueous solution of zinc sulfate, and the separator is glass fiber GF-a, which was found to have good cycling performance by cycling tests. After disassembling the cell, it was found that dendrites were not found in the negative electrode.
Example 15
This example provides a battery including a positive electrode, a negative electrode, an electrolyte, and a separator, where the positive electrode is ammonium vanadate, the negative electrode is the Zn-TCPP-modified zinc negative electrode of example 5, the electrolyte is an ethylene glycol solution of zinc trifluoromethanesulfonate, and the separator is glass fiber GF-B, and cycle tests show that the battery has good cycle performance. After disassembling the cell, it was found that dendrites were not found in the negative electrode.
Example 16
This example provides a battery, which includes a positive electrode, a negative electrode, an electrolyte, and a separator, where the positive electrode is ammonium vanadate, the negative electrode is the Zn-TCPP-modified zinc negative electrode of example 6, the electrolyte is an ethanol solution of zinc trifluoromethanesulfonate, and the separator is glass fiber GF-C, and cycle tests show that the battery has good cycle performance. After disassembling the cell, it was found that dendrites were not found in the negative electrode.
Example 17
This example provides a battery including a positive electrode, a negative electrode, an electrolyte, and a separator, wherein the positive electrode is ammonium vanadate, the negative electrode is the Zn-TCPP modified zinc negative electrode of example 7, the electrolyte is an ethanol solution of zinc sulfate, and the separator is glass fiber GF-C, which was found to have good cycling performance by cycling tests. After disassembling the cell, it was found that dendrites were not found in the negative electrode.
Example 18
This example provides a battery including a positive electrode, a negative electrode, an electrolyte, and a separator, wherein the positive electrode is ammonium vanadate, the negative electrode is the Zn-TCPP modified zinc negative electrode of example 8, the electrolyte is a solution of zinc sulfate in ethylene glycol, and the separator is glass fiber GF-D, which was found to have good cycling performance by cycling tests. After disassembling the cell, it was found that dendrites were not found in the negative electrode.
Example 19
This example provides a battery including a positive electrode, a negative electrode, an electrolyte, and a separator, where the positive electrode is ammonium vanadate, the negative electrode is the Zn-TCPP-modified zinc negative electrode of example 9, the electrolyte is an ethanol solution of zinc sulfate, and the separator is glass fiber GF-C, which is found through cycle tests to have good cycle performance. After disassembling the cell, it was found that dendrites were not found in the negative electrode.
Example 20
This example provides a battery, which includes a positive electrode, a negative electrode, an electrolyte, and a separator, wherein the positive electrode is ammonium vanadate, the negative electrode is the Zn-TCPP modified zinc negative electrode of example 10, the electrolyte is an aqueous solution of zinc sulfate, and the separator is a cellulose separator, and cycle tests show that the battery has good cycle performance. After disassembling the cell, it was found that dendrites were not found in the negative electrode.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. A method of synthesizing a porphyrin-based two-dimensional metal-organic framework nanosheet array on a zinc substrate, comprising at least the steps of:
step one, preparing a solution: dispersing a precursor of a porphyrin structure containing carboxyl in a mixed solvent to obtain a precursor solution;
secondly, reacting the precursor solution with a zinc substrate to obtain a porphyrin-based two-dimensional Zn-MOF array;
and thirdly, washing the porphyrin-based two-dimensional Zn-MOF array obtained in the second step by using a solvent, and then removing the solvent, so that the porphyrin-based two-dimensional MOF nanosheet array is attached to the zinc substrate.
2. The method of synthesizing an array of porphyrin-based two-dimensional metal-organic framework nanosheets on a zinc substrate of claim 1, wherein the array of porphyrin-based two-dimensional MOF nanosheets has an adjustable open-cell structure; and the nano-sheets in the porphyrin-based two-dimensional MOF nano-sheet array are vertical to the zinc substrate, and the porphyrin-based two-dimensional MOF nano-sheet array has abundant channel transmission ions.
3. The method of synthesizing an array of porphyrin-based two-dimensional metal-organic framework nanosheets on a zinc substrate of claim 1, wherein the metal center in the array of porphyrin-based two-dimensional MOF nanosheets is zinc.
4. The method for synthesizing a porphyrin-based two-dimensional metal organic framework nanosheet array on a zinc substrate according to claim 2, wherein the pore size of the open pore structure of the porphyrin-based two-dimensional MOF nanosheet array is from 100 nm to 2 μ ι η, the thickness of the nanosheet is from 10 nm to 100 nm, and the thickness of the porphyrin-based two-dimensional metal organic framework nanosheet array is from 5 μ ι η to 800 μ ι η.
5. The method for synthesizing a porphyrin-based two-dimensional metal organic framework nanosheet array on a zinc substrate as recited in claim 1, wherein the mixed solvent of the first step is at least two of dimethylformamide, ethanol, methanol, ethylene glycol, methyl pyrrolidone, and dimethyl sulfoxide.
6. Synthetic porphyrin-based two-dimensional metal-organic framework nanosheets on a zinc substrate according to claim 1The array method is characterized in that in the second step, the temperature range of the reaction is 25-180 DEGoAnd C, the reaction time is 1min-24 h.
7. The method for synthesizing a porphyrin-based two-dimensional metal organic framework nanosheet array on a zinc substrate as recited in claim 1, wherein the precursor of the porphyrin structure containing carboxyl groups is 4,4,4,4- (porphyrin-5, 10,15, 20-tetracarboxyl) tetra (benzoic acid), and the concentration of the precursor solution is 1-1000 mg ml-1。
8. The method for synthesizing an array of porphyrin-based two-dimensional metal-organic framework nanosheets on a zinc substrate according to claim 1, wherein the third step the solvent is at least one of ethanol, water, methanol, and petroleum ether.
9. The battery comprises a positive electrode, a negative electrode, electrolyte and a separation film, and is characterized in that: the negative electrode is a zinc-based porphyrin-based two-dimensional MOF nanosheet array prepared by the method of any one of claims 1-8.
10. The battery of claim 9, wherein: the positive electrode is a vanadium-based positive electrode, a manganese-based positive electrode or Prussian blue.
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