Method for designing high-voltage positive electrode material through molecular energy orbit regulation and control, covalent organic framework material, battery positive electrode and preparation method thereof, and aqueous zinc-organic battery

Abstract

The invention provides a method for designing a high-voltage positive electrode material through molecular energy track regulation and control, a covalent organic framework material, a battery positive electrode, a preparation method of the battery positive electrode and an aqueous zinc-organic battery, and belongs to the technical field of chemical power sources. An organic donor / acceptor molecule with the lowest molecular energy level is obtained through density functional theory simulation evaluation and comparison, and then the organic donor molecule and the organic acceptor molecule react to obtain the covalent organic framework material. Then weighing a covalent organic framework material, a conductive agent and an adhesive, adding ethanol, uniformly grinding to obtain slurry, coating a current collector with the slurry, drying to obtain a battery positive electrode, and finally assembling the battery positive electrode with a zinc foil negative electrode, an electrolyte and a battery shell to prepare the aqueous zinc-organic battery. As the used covalent organic framework material has low molecular energy level, highly conjugated porous planar configuration and high-density active sites, the prepared battery shows high discharge voltage, high energy density and excellent cycle stability.

Description

Technical Field

[0001] This invention belongs to the field of chemical power source technology, specifically relating to a method for designing high-voltage cathode materials by molecular energy orbital regulation, covalent organic framework materials and battery cathodes and their preparation methods, and aqueous zinc-organic batteries. Background Technology

[0002] With the increasing demand for large-scale energy storage, aqueous zinc-organic batteries have become a highly promising candidate for energy storage technology due to the advantages of zinc anodes, such as high cost-effectiveness, low redox potential, and high theoretical capacity, as well as the characteristics of organic cathode materials, such as strong sustainability and flexible structural and functional design.

[0003] To develop high-performance aqueous zinc-organic batteries, researchers are dedicated to optimizing organic cathode materials. Aromatic organic small molecules, rich in high-density redox active functional groups, can provide high capacity, but they are easily soluble in aqueous electrolytes, resulting in short battery cycle life (usually less than 10,000 cycles). While polymerizing them into insoluble polymers can improve resistance to dissolution, the twisted molecular chains block active sites, leading to insufficient capacity utilization (usually below 300 mAh / g). Strategies that construct supramolecular or polymeric superstructures face significant design and manufacturing challenges.

[0004] Covalent organic framework materials, with their ordered nanoporous channels, periodically arranged redox active sites, π-conjugated donor-acceptor structure, and tunable function, have become ideal alternatives that balance the high activity of small molecules with the insolubility of polymers. They have been used to prepare aqueous zinc-organic battery cathodes with capacities of 200 mAh / g to 300 mAh / g and cycle lives of up to 20,000 cycles. However, the high HOMO / LUMO levels of the electroactive donor / acceptor units in existing covalent organic framework materials result in low redox potentials (below 0.8 V vs. Zn). 2+ / Zn), creating a tricky trade-off between capacity and voltage, which limits the improvement of energy density of aqueous zinc organic batteries (below 300 Wh / kg).

[0005] Theoretically, lowering the HOMO / LUMO energy level can increase the redox potential. However, it has not yet been realized to break the potential bottleneck without compromising the multi-redox capabilities of covalent organic framework materials by strategically pairing low HOMO / LUMO donor / acceptor units. Therefore, it is urgent to develop a new molecular design method to solve the key problem of capacity-voltage imbalance in existing aqueous zinc organic battery electrode materials. Summary of the Invention

[0006] This invention is made to solve the above-mentioned problems, and aims to provide a method for designing high-voltage cathode materials by controlling molecular energy orbitals, covalent organic framework materials and battery cathodes and their preparation methods, and aqueous zinc-organic batteries.

[0007] This invention provides a method for designing high-voltage cathode materials using molecular energy orbital modulation, characterized by the following steps: A10, evaluating the HOMO energy level of the functional groups of the electron donor unit used for the redox reaction of the battery, and evaluating the LUMO energy level of the functional groups of the electron acceptor unit used for the redox reaction of the battery, based on density functional theory simulation; A20, selecting the functional groups of the electron donor unit used for the redox reaction of the battery with the lowest HOMO energy level as the core electron donor unit, and selecting the functional groups of the electron acceptor unit used for the redox reaction of the battery with the lowest LUMO energy level as the core electron acceptor unit; A30, using the compound with the core electron acceptor unit as the organic acceptor molecule of the high-voltage cathode material, and using the compound with the core electron donor unit as the organic donor molecule of the high-voltage cathode material, wherein the high-voltage cathode material is used as a precursor for the active material of the cathode of an aqueous zinc-organic battery.

[0008] The method for designing high-voltage cathode materials by molecular energy orbital modulation provided by the present invention may also have the following features: In step A10, the functional groups of the electron donor unit used for the redox reaction of the battery include imine, tertiary nitrogen, phosphorus, and trithiophene, and the functional groups of the electron acceptor unit used for the redox reaction of the battery include carbonyl, nitro, azo, triazine, and tricyano; In step A20, the core electron donor unit is trithiophene, and the core electron acceptor unit is tricyano; In step A30, the organic donor molecule is benzo[1,2-b:3,4-b'':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde, and the organic acceptor molecule is 2,4,6-tricyano-1,3,5-trimethylbenzene.

[0009] This invention also provides a method for preparing a covalent organic framework material, characterized by using the aforementioned method for designing high-voltage cathode materials with molecular energy orbital modulation, comprising the following steps: B10, dissolving the high-voltage cathode material containing organic acceptor molecules and organic donor molecules in N,N-dimethylformamide and piperidine to obtain a mixture; B20, freezing the mixture with liquid nitrogen and placing it in a vacuum environment; B30, heating the product of step B20 to obtain a solid; B40, filtering, washing, and drying the solid to obtain the covalent organic framework material, wherein the covalent organic framework material is used to coat the cathode of an aqueous zinc-organic battery, and when the organic donor molecule is benzo[1,2-b:3,4-b'':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde and the organic acceptor molecule is 2,4,6-tricyano-1,3,5-trimethylbenzene, the heating temperature in step B30 is 120 ℃~180 ℃. At ℃, the heating time is 36h~120h, and the solid is reddish-brown.

[0010] The method for preparing covalent organic framework materials provided by the present invention may also have the following feature: in step B10, when the organic donor molecule is benzo[1,2-b:3,4-b'':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde and the organic acceptor molecule is 2,4,6-tricyano-1,3,5-trimethylbenzene, the mass ratio of the organic donor molecule to the organic acceptor molecule is 1:(0.6~2.0).

[0011] The method for preparing covalent organic framework materials provided by the present invention may also have the following feature: in step B10, the volume ratio of N,N-dimethylformamide and piperidine is 1:(0.03~0.06).

[0012] The method for preparing covalent organic framework materials provided by the present invention may also have the following features: in step B40, tetrahydrofuran and methanol are used for washing, and the drying method is vacuum drying at 60℃~80℃ for 6h~36h.

[0013] Preferably, in step B40, the drying method is vacuum drying at 80°C for 12 hours.

[0014] The present invention also provides a covalent organic framework material, characterized by being prepared by any of the preceding methods for preparing covalent organic framework materials, wherein the covalent organic framework material has low HOMO / LUMO molecular energy levels, with its HOMO molecular energy level ranging from -6 eV to -4.8 eV and its LUMO molecular energy level ranging from -4.2 to -2 eV, the covalent organic framework material has a narrow molecular energy level difference ranging from 1.8 eV to 3 eV, and the covalent organic framework material has a highly conjugated porous planar configuration and a high density of active sites.

[0015] The present invention also provides a method for preparing a battery positive electrode, characterized by using the aforementioned covalent organic framework material to prepare a battery positive electrode for an aqueous zinc-organic battery, comprising the following steps: C10, mixing and grinding the covalent organic framework material, conductive agent, binder and ethanol to obtain a slurry; C20, coating the slurry onto a current collector and drying it to obtain a battery positive electrode.

[0016] Preferably, in step C10, the conductive agent is graphite and the adhesive is polytetrafluoroethylene.

[0017] Preferably, in step C10, the mass ratio of the covalent organic framework material, the conductive agent, and the adhesive is 6:3:1.

[0018] Preferably, in step C20, the current collector is titanium foil, nickel mesh, titanium mesh, stainless steel mesh, or carbon paper.

[0019] The present invention also provides a battery positive electrode, which is prepared by the aforementioned method for preparing a battery positive electrode and is used in an aqueous zinc-organic battery.

[0020] The present invention also provides an aqueous zinc-organic battery, characterized by comprising a battery casing, a battery positive electrode, a battery negative electrode, an electrolyte, and a battery separator, wherein the battery positive electrode is the aforementioned battery positive electrode, the battery negative electrode is Zn, and the electrolyte is an aqueous solution of any one or more of NH4CF3SO3, (NH4)2SO4, HCF3SO3, or Zn(CF3SO3)2.

[0021] Preferably, the negative electrode of the battery is a high-purity commercial zinc foil with a Zn content of ≥99.99%.

[0022] Preferably, the electrolyte concentration in the electrolyte solution is 1 mol / L to 10 mol / L.

[0023] Preferably, the battery separator is filter paper or glass fiber.

[0024] Preferably, the battery casing is a CR2032 button battery casing.

[0025] The beneficial effects of this invention are:

[0026] (1) Through molecular energy level regulation strategy, covalent organic framework materials have low HOMO / LUMO molecular energy levels and narrow molecular energy level difference, which endows the cathode material with a flat high redox potential and significantly improves the output voltage level of the battery.

[0027] (2) Covalent organic framework materials have highly conjugated porous planar configurations and high-density active sites, which can provide more exposed built-in thiophene / cyano active sites and ultra-low redox reaction energy barriers. They can also provide excellent electrical conductivity and strong resistance to dissolution, achieving high charge transfer efficiency and lower kinetic resistance.

[0028] (3) When covalent organic framework materials are used as positive electrode active materials, two-step CF3SO3 is achieved with low activation energy. - / NH4 + The charge storage mechanism fully utilizes thiophene / cyano groups, resulting in a battery exhibiting high specific capacity, energy density, and excellent cycle stability. This molecular energy level modulation strategy helps address the problems of low voltage and capacity and insufficient utilization of active sites in traditional COF materials.

[0029] (4) The main raw materials used in this invention are abundant, cost-effective and environmentally friendly. The entire system of electrode and electrolyte preparation process is completed at room temperature and pressure. The preparation steps are simple, the operating conditions are mild and there is no environmental burden. Attached Figure Description

[0030] Figure 1 This is a flowchart illustrating the preparation method of covalent organic framework materials according to an embodiment of the present invention.

[0031] Figure 2 This is a comparison diagram of molecular energy level evaluation in step A10 of an embodiment of the present invention.

[0032] Figure 3 These are the structural formulas of the covalent organic framework materials used in the embodiments and comparative examples of this invention, along with their corresponding infrared and nuclear magnetic resonance spectra.

[0033] Figure 4 These are molecular energy level diagrams of the covalent organic framework materials in the embodiments and comparative examples of the present invention.

[0034] Figure 5 This is a scanning electron microscope image of a covalent organic framework material according to an embodiment of the present invention.

[0035] Figure 6 This is a transmission electron microscope image of a covalent organic framework material according to an embodiment of the present invention.

[0036] Figure 7 This is a cyclic voltammetry diagram of an aqueous zinc-organic battery according to an embodiment of the present invention.

[0037] Figure 8 These are constant current charge-discharge test diagrams of aqueous zinc-organic batteries used in embodiments and comparative examples of the present invention.

[0038] Figure 9This is a cycle stability diagram of aqueous zinc-organic batteries of the embodiments and comparative examples of the present invention at a current density of 10 A / g.

[0039] Figure 10 This is an energy density diagram of an aqueous zinc-organic battery according to an embodiment of the present invention. Detailed Implementation

[0040] To make the technical means, creative features, objectives and effects of this invention easy to understand, the following embodiments, in conjunction with the accompanying drawings, specifically illustrate a method for designing high-voltage cathode materials by molecular energy orbital modulation, covalent organic framework materials and battery cathodes and their preparation methods, and aqueous zinc-organic batteries.

[0041] <Example>

[0042] This embodiment provides a method for designing high-voltage cathode materials by controlling molecular energy orbitals, including the following steps A10~A30:

[0043] A10, based on density functional theory simulations, evaluates the HOMO energy levels of functional groups in electron donor units used for redox reactions in batteries, and evaluates the LUMO energy levels of functional groups in electron acceptor units used for redox reactions in batteries.

[0044] Specifically, in this embodiment, the functional groups of the electron donor unit used for the redox reaction of the battery include imine, tertiary nitrogen, phosphorus, and trithiophene; the functional groups of the electron acceptor unit used for the redox reaction of the battery include carbonyl, nitro, azo, triazine, and tricyano.

[0045] A20, the functional group with the lowest HOMO energy level among the electron donor units used for the redox reaction of the battery is selected as the core electron donor unit, and the functional group with the lowest LUMO energy level among the electron acceptor units used for the redox reaction of the battery is selected as the core electron acceptor unit.

[0046] Specifically, in this embodiment, the core electron donor unit is trithiophene and the core electron acceptor unit is tricyano.

[0047] A30 refers to organic acceptor molecules that use compounds with core electron acceptor units as high-voltage cathode materials, and organic donor molecules that use compounds with core electron donor units as high-voltage cathode materials.

[0048] Specifically, in this embodiment, the selected organic donor molecule is benzo[1,2-b:3,4-b'':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde, and the organic acceptor molecule is 2,4,6-tricyano-1,3,5-trimethylbenzene.

[0049] Among them, high-voltage cathode materials are used as precursors for active materials in aqueous zinc-organic batteries.

[0050] This embodiment also provides a covalent organic framework material with low HOMO / LUMO molecular energy levels, wherein the HOMO molecular energy level is -6eV to -4.8eV and the LUMO molecular energy level is -4.2 to -2eV; the covalent organic framework material has a narrow molecular energy level difference, ranging from 1.8eV to 3eV; and the covalent organic framework material has a highly conjugated porous planar configuration and a high density of active sites.

[0051] Figure 1 This is a flowchart illustrating the preparation method of covalent organic framework materials according to an embodiment of the present invention.

[0052] like Figure 1 As shown, the method for preparing the covalent organic framework material in this embodiment uses the aforementioned method for designing high-voltage cathode materials by controlling molecular energy orbitals, and includes the following steps B10~B40:

[0053] B10 is a high-voltage cathode material containing an organic acceptor molecule (2,4,6-tricyano-1,3,5-trimethylbenzene) and an organic donor molecule (benzo[1,2-b:3,4-b'':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde) in a mass ratio of (0.6~2.0):1, dissolved in a solution of N,N-dimethylformamide and piperidine in a volume ratio of 1:(0.03~0.06), and ultrasonically reacted at 25°C for 10 min to obtain a mixed solution.

[0054] Specifically, in this embodiment, 9.75 mg of 2,4,6-tricyano-1,3,5-trimethylbenzene and 16.5 mg of benzo[1,2-b:3,4-b'':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde were weighed; N,N-dimethylformamide and piperidine were 1 mL and 0.03 mL, respectively.

[0055] B20 involves placing the mixture in a high-temperature and pressure-resistant glass tube, rapidly freezing it in a liquid nitrogen bath, then evacuating it to an internal pressure of 0.5 mbar and sealing it with a flame.

[0056] B30: After heating the high-temperature and pressure-resistant glass tube from step B20 to room temperature, place it in an oven at 120 ℃~180 ℃ for 72 h to produce a reddish-brown solid.

[0057] B40, a high-temperature and pressure-resistant glass tube containing a reddish-brown solid was broken at the neck, the reddish-brown solid was separated by centrifugation, and finally washed three times with tetrahydrofuran and methanol. The powder was collected and dried in an oven at 80 °C for 12 h to obtain a trithiophene tricyano covalent organic framework material.

[0058] This embodiment also provides a battery cathode for use in an aqueous zinc-organic battery. Its preparation method utilizes the aforementioned covalent organic framework material and includes the following steps:

[0059] C10, trithiophene tricyano covalent organic framework material, graphite conductive agent, and polytetrafluoroethylene adhesive were weighed in a mass ratio of 6:3:1, and ethanol was added before uniform grinding to obtain a slurry.

[0060] C20, the slurry is evenly coated onto the stainless steel mesh current collector and dried to obtain the positive electrode of the battery.

[0061] This embodiment also provides an aqueous zinc-organic battery, including a battery casing, a positive electrode, a negative electrode, an electrolyte, and a battery separator.

[0062] The battery casing is a CR2032 button cell battery casing; the positive electrode is the positive electrode of the battery prepared in the above embodiment; the negative electrode is a commercially available high-purity zinc foil with a Zn content ≥99.99%; the electrolyte is a 3mol / L NH4CF3SO3 water solution; and the battery separator is a GE-Whatman glass fiber separator.

[0063] <Comparative Example>

[0064] This comparative example provides a method for preparing a covalent organic framework material with a wide molecular energy level difference, and based on this covalent organic framework material, a battery cathode and an aqueous zinc-organic battery are prepared according to the corresponding examples.

[0065] The preparation method of the covalent organic framework material in this comparative example is generally similar to that in the examples, except that the core electron acceptor unit in the comparative example uses a triazine molecule with the highest LUMO value.

[0066] Specifically, the preparation method of the covalent organic framework material with a wide molecular energy level difference in this comparative example differs from that in the examples in the following ways:

[0067] In step B10:

[0068] (1) 16.5 mg of benzo[1,2-b:3,4-b'':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde was used as an organic donor molecule, and 6.2 mg of 2,4,6-trimethyl-1,3,5-triazine was used as an organic acceptor molecule.

[0069] (2) Take 0.45 mL of mesitylene, 0.45 mL of 1,4-dioxane, 0.2 mL of trifluoroacetic acid (6 mol / L) and 0.025 mL of acetonitrile in sequence.

[0070] (3) Benzo[1,2-b:3,4-b'':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde and 2,4,6-trimethyl-1,3,5-triazine were added to a 10 mL high-temperature and pressure-resistant glass tube, followed by the addition of mesitylene, 1,4-dioxane, trifluoroacetic acid, and acetonitrile to obtain a mixed solution. After ultrasonic reaction at 25°C for 10 min, the high-temperature and pressure-resistant glass tube was rapidly frozen in a liquid nitrogen bath, evacuated to an internal pressure of 0.5 mbar, and flame-sealed. The sealed glass tube was then removed, heated to room temperature, and placed in an oven at 180°C for 72 h, producing a yellow solid.

[0071] Steps B20-B40, the preparation method of the battery positive electrode, and the preparation method of the aqueous zinc-organic battery are largely similar to those in the examples and will not be repeated here.

[0072] The purpose of providing this comparative example of a covalent organic framework material with a wide molecular energy level difference, its corresponding battery cathode, and an aqueous zinc-organic battery is to compare the electrochemical performance of the aqueous zinc-organic batteries in the examples and the comparative example for subsequent test cases. The focus is on examining the differences in electrochemical performance between the trithiophene triazine-based covalent organic framework material with a high LUMO value as the cathode active material and the trithiophene tricyano-based covalent organic framework cathode material used in the examples. Through comparative experiments in subsequent test cases, the performance differences of organic cathodes under conditions of controlled molecular energy levels can be clearly defined, providing strong evidence for evaluating the superiority of the present invention.

[0073] <Test Example>

[0074] This test case examines the covalent organic framework materials, battery cathodes, or aqueous zinc-organic batteries used in the examples and / or comparative examples. The battery energy storage performance was tested using a CHI660E electrochemical workstation, while the battery cycle and rate performance were tested using a LAND CT2001A battery testing system. The voltage window was 0.2 V to 1.5 V.

[0075] Figure 2 This is a comparison diagram of molecular energy level evaluation in step A10 of an embodiment of the present invention.

[0076] like Figure 2As shown, based on density functional theory simulations, the HOMO and LUMO levels of the organic donor / acceptor units can be evaluated. The tricyano molecule has the lowest LUMO level (-3.82 eV), and this structure can impart the optimal reduction potential to the cathode material; therefore, the tricyano group was selected as the core electron acceptor unit. The trithiophene molecule has the lowest HOMO level (-6.04 eV), which can ensure the high oxidation potential of the cathode material; therefore, the trithiophene molecule was selected as the core electron donor unit. Meanwhile, the triazine molecule has the highest LUMO level (-1.75 eV), and the triazine molecule was selected as the electron acceptor unit in the comparative example.

[0077] Figure 3 These are the structural formulas of the covalent organic framework materials used in the embodiments and comparative examples of this invention, along with their corresponding infrared and nuclear magnetic resonance spectra.

[0078] like Figure 3 As shown, in the examples, benzo[1,2-b:3,4-b'':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde and 2,4,6-tricyano-1,3,5-trimethylbenzene were linked by olefin bonds after reaction to form a covalent organic framework material. In the comparative example, benzo[1,2-b:3,4-b'':5,6-b'']trithiophene-2,5,8-tricarboxaldehyde and 2,4,6-trimethyl-1,3,5-triazine were linked by olefin bonds after reaction to form the covalent organic framework material in the comparative experiment. Infrared spectroscopy and nuclear magnetic resonance spectroscopy both confirmed the successful synthesis of the covalent organic framework materials in the examples and comparative examples.

[0079] Figure 4 These are molecular energy level diagrams of the covalent organic framework materials in the embodiments and comparative examples of the present invention.

[0080] like Figure 4 As shown, the trithiophene tricyano covalent organic framework material in the embodiments exhibits a lower LUMO / HOMO energy level and a narrower energy level difference compared to the material in the comparative examples. This is beneficial for improving the redox activity, high redox potential, and low electron transport barrier of the cathode material, thereby enhancing the overall performance of the battery. These test results provide an important reference for selecting the optimal cathode material.

[0081] Figure 5 This is a scanning electron microscope image of a covalent organic framework material according to an embodiment of the present invention.

[0082] like Figure 5 As shown, the trithiophene tricyano covalent organic framework material prepared in the examples exhibits a nanoparticle structure.

[0083] Figure 6 This is a transmission electron microscope image of a covalent organic framework material according to an embodiment of the present invention.

[0084] like Figure 6 As shown, the trithiophene tricyano covalent organic framework material prepared in the examples exhibits obvious lattice fringes with a lattice fringe spacing of 0.34 nm, indicating that the trithiophene tricyano covalent organic framework material has good crystallinity.

[0085] Figure 7 This is a cyclic voltammetry diagram of an aqueous zinc-organic battery according to an embodiment of the present invention.

[0086] like Figure 7 As shown, the cathode material of the aqueous zinc-organic battery in the embodiment exhibits two distinct redox peaks, indicating that the cathode material undergoes a two-step redox process.

[0087] Figure 8 These are constant current charge-discharge test diagrams of aqueous zinc-organic batteries used in embodiments and comparative examples of the present invention.

[0088] like Figure 8 As shown, the aqueous zinc-organic battery prepared in the example has a specific capacity of over 335 mAh / g and a high average discharge voltage (1.2V) when charged and discharged at 0.2A / g. Compared with the cathode material of the aqueous zinc-organic battery in the comparative example (268 mAh / g, 0.9V), it exhibits higher specific capacity storage performance and higher voltage output level.

[0089] Figure 9 This is a cycle stability diagram of aqueous zinc-organic batteries of the embodiments and comparative examples of the present invention at a current density of 10 A / g.

[0090] like Figure 9 As shown, the aqueous zinc-organic battery assembled in the embodiment retains 89.1% of its capacity after 70,000 charge-discharge cycles, which is superior to the aqueous zinc-organic battery assembled with the cathode material in the comparative example (71.2%).

[0091] Figure 10 This is an energy density diagram of an aqueous zinc-organic battery according to an embodiment of the present invention.

[0092] like Figure 10 As shown, the zinc-organic battery assembled in the examples exhibits a high energy density (402 Wh / kg). Compared to the energy density of the aqueous zinc-organic battery assembled in the comparative example, the zinc-organic battery assembled in the examples exhibits superior energy storage capacity.

[0093] Those skilled in the art should understand that this invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to this invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method of designing high-voltage cathode materials by molecular energy orbital regulation, characterized in that, comprising the following steps: A10, based on density functional theory simulation, evaluating the HOMO energy level of the functional group of the electron donor unit for the battery redox reaction, evaluating the LUMO energy level of the functional group of the electron acceptor unit for the battery redox reaction; A20, selecting the functional group with the lowest HOMO energy level in the electron donor unit for the battery redox reaction as the core electron donor unit, and selecting the functional group with the lowest LUMO energy level in the electron acceptor unit for the battery redox reaction as the core electron acceptor unit; A30, taking the compound with the core electron acceptor unit as an organic acceptor molecule of a high-voltage positive electrode material, and taking the compound with the core electron donor unit as an organic donor molecule of a high-voltage positive electrode material, wherein the high-voltage positive electrode material is used as a precursor of an active material of a battery positive electrode of a water-based zinc-organic battery.

2. The method for designing a high-voltage positive electrode material by regulating molecular energy orbitals according to claim 1, characterized in that: wherein in step A10, the functional group of the electron donor unit for the battery redox reaction includes imine group, tertiary nitrogen group, phosphorus group, and tri-thiophene group, and the functional group of the electron acceptor unit for the battery redox reaction includes carbonyl group, nitro group, azo group, triazine group, and tri-cyan group; in step A20, the core electron donor unit is tri-thiophene group, and the core electron acceptor unit is tri-cyan group; in step A30, the organic donor molecule is benzo[1,2-b:3,4-b'':5,6-b''] tri-thiophene-2,5,8-tricarboxaldehyde, and the organic acceptor molecule is 2,4,6-tricyano-1,3,5-trimethylbenzene.

3. A method of preparing a covalent organic framework material, characterized in that, The high-voltage positive electrode material designed by the method for designing a high-voltage positive electrode material by regulating molecular energy orbitals according to claim 1 or 2 comprises the following steps: B10, dissolving the high-voltage positive electrode material containing the organic acceptor molecule and the organic donor molecule in N,N-dimethylformamide and piperidine to obtain a mixed solution; B20, liquid nitrogen freezing the mixed solution and placing it in a vacuum environment; B30, heating the product of step B20 to obtain a solid; B40, filtering, washing, and drying the solid to obtain a covalent organic framework material, wherein the covalent organic framework material is used for coating on a battery positive electrode of a water-based zinc-organic battery, when the organic donor molecule is benzo[1,2-b:3,4-b'':5,6-b''] tri-thiophene-2,5,8-tricarboxaldehyde and the organic acceptor molecule is 2,4,6-tricyano-1,3,5-trimethylbenzene, the heating temperature in step B30 is 120-180°C, the heating time is 36-120h, and the solid is red-brown.

4. The method for preparing a covalent organic framework material according to claim 3, characterized in that: wherein in step B10, when the organic donor molecule is benzo[1,2-b:3,4-b'':5,6-b''] tri-thiophene-2,5,8-tricarboxaldehyde and the organic acceptor molecule is 2,4,6-tricyano-1,3,5-trimethylbenzene, The mass ratio of the organic donor molecule to the organic acceptor molecule is 1:(0.6-2.0).

5. The method of claim 3, wherein the covalent organic framework material is prepared by the method comprising the following steps: B10, B20, B30, B40, B50, B60, B70, B80, B90, B100, B110, B120, B130, B140, B150, B160, B170, B180, B190, B200, B210, B220, B230, B240, B250, B260, B270, B280, B290, B300, B310, B320, B330, B340, B350, B360, B370, B380, B390, B400, B410, B420, B430, B440, B450, B460, B470, B480, B490, B500, B510, B520, B530, B540, B550, B560, B570, B580, B590, B600, B610, B620, B630, B640, B650, B660, B670, B680, B690, B700, B710, B720, B730, B740, B750, B760, B770, B780, B790, B800, B810, B820, B830, B840, B850, B860, B870, B880, B890, B900, B910, B920, B930, B940, B950, B960, B970, B980, B990, B1000, B1010, B1020, B1030, B1040, B1050, B1060, B1070, B1080, B1090, B1100, B1110, B1120, B1130, B1140, B1150, B1160, B1170, B1180, B1190, B1200, B1210, B1220, B1230, B1240, B1250, B1260, B1270, B1280, B1290, B1300, B1310, B1320, B1330, B1340, B1350, B1360, B1370, B1380, B1390, B1400, B1410, B1420, B1430, B1440, B1450, B1460, B1470, B1480, B1490, B1500, B1510, B1520, B1530, B1540, B1550, B1560, B1570, B1580, B1590, B1600, B1610, B1620, B1630, B1640, B1650, B1660, B1670, B1680, B1690, B1700, B1710, B1720, B1730, B1740, B1750, B1760, B1770, B1780, B1790, B1800, B1810, B1820, B1830, B1840, B1850, B1860, B1870, B1880, B1890, B1900, B1910, B1920, B1930, B1940, B1950, B1960, B1970, B1980, B1990, B2000, B2010, B2020, B2030, B2040, B2050, B2060, B2070, B2080, B2090, B2100, B2110, B2120, B2130, B2140, B2150, B2160, B2170, B2180, B2190, B2200, B2210, B2220, B2230, B2240, B2250, B2260, B2270, B2280, B2290, B2300, B2310, B2320, B2330, B2340, B2350, B2360, B2370, B2380, B2390, B2400, B2410, B2420, B2430, B2440, B2450, B2460, B2470, B2480, B2490, B2500, B2510, B2520, B2530, B2540, B2550, B2560, B2570, B2580, B2590, B2600, B2610, B2620, B2630, B2640, B2650, B2660, B2670, B2680, B2690, B2700, B2710, B2720, B2730, B2740, B2750, B2760, B2770, B2780, B2790, B2800, B2810, B2820, B2830, B2840, B2850, B2860, B2870, B2880, B2890, B2900, B2910, B2920, B2930, B2940, B2950, B2960, B2970, B2980, B2990, B3000, B3010, B3020, B3030, B3040, B3050, B3060, B3070, B3080, B3090, B3100, B3110, B3120, B3130, B3140, B3150, B3160, B3170, B3180, B3190, B3200, B3210, B3220, B3230, B3240, B3250, B3260, B3270, B3280, B3290, B3300, B3310, B3320, B3330, B3340, B3350, B3360, B3370, B3380, B3390, B3400, B3410, B3420, B3430, B3440, B3450, B3460, B3470, B3480, B3490, B3500, B3510, B3520, B3530, B3540, B3550, B3560, B3570, B3580, B3590, B3600, B3610, B3620, B3630, B3640, B3650, B3660, B3670, B3680, B3690, B3700, B3710, B3720, B3730, B3740, B3750, B3760, B3770, B3780, B3790, B3800, B3810, B3820, B3830, B3840, B3850, B3860, B3870, B3880, B3890, B3900, B3910, B3920, B3930, B3940, B3950, B3960, B3970, B3980, B3990, B4000, B4010, B4020, B4030, B4040, B4050, B4060, B4070, B4080, B4090, B4100, B4110, B4120, B4130, B4140, B4150, B4160, B4170, B4180, B4190, B4200, B4210, B4220, B4230, B4240, B4250, B4260, B4270, B4280, B4290, B4300, B4310, B4320, B4330, B4340, B4350, B4360, B4370, B4380, B4390, B4400, B4410, B4420, B4430, B4440, B4450, B4460, B4470, B4480, B4490, B4500, B4510, B4520, B4530, B4540, B4550, B4560, B4570, B4580, B4590, B4600, B4610, B4620, B4630, B4640, B4650, B4660, B4670, B4680, B4690, B4700, B4710, B4720, B4730, B4740, B4750, B4760, B4770, B4780, B4790, B4800, B4810, B4820, B4830, B4840, B4850, B4860, B4870, B4880, B4890, B4900, B4910, B4920, B4930, B4940, B4950, B4960, B4970, B4980, B4990, B5000, B5010, B5020, B5030, B5040, B5050, B5060, B5070, B5080, B5090, B5100, B5110, B5120, B5130, B5140, B5150, B5160, B5170, B5180, B5190, B5200, B5210, B5220, B5230, B524 wherein ​ ​ wherein, ​ 7. A covalent organic framework material characterized in that, ​ ​ ​ ​ 8. A method for producing a battery positive electrode, characterized by, ​ ​ ​ 9. A battery positive electrode, characterized by, ​ 10. An aqueous zinc-organic battery, characterized in that, ​ ​ ​ ​

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