Preparation method of nanosheet-organic active molecule-catalyst hybrid material and application thereof in photoelectric storage integrated battery

Abstract

This invention discloses a method for preparing a nanosheet-organic active molecule-catalyst hybrid material and its application in an integrated photovoltaic-energy storage battery. The preparation method includes: adding organic active molecules to an organic dispersion containing nanosheets and ultrasonically dispersing them, allowing the organic active molecules to intercalate into the nanosheets, resulting in a nanosheet-organic molecule mixed dispersion; adding a crosslinking agent, and under the action of a first catalyst, covalently crosslinking the nanosheets and organic active molecules; and physically mixing the separated nanosheet-organic electrode material with a second catalyst to obtain the nanosheet-organic active molecule-catalyst hybrid material. This invention is the first to introduce a single-atom or diatomic catalyst into a zinc-ion battery, which can reduce the polarization potential of the zinc-ion battery, improve its cycle life, and be used as an energy storage electrode in an integrated photovoltaic-energy storage battery to accelerate the storage rate of photogenerated charge and improve the overall conversion efficiency of the integrated photovoltaic-energy storage battery.

Description

Technical Field

[0001] This invention relates to the field of self-powered technology, and more specifically, to a method for preparing a nanosheet-organic active molecule-catalyst hybrid material and its application in an integrated photovoltaic-storage battery. Background Technology

[0002] Photovoltaic-storage integrated batteries based on zinc-ion batteries not only require zinc-ion batteries to have a fast charge storage rate for photogenerated charges, but also a long cycle life. Although nanosheet-organic electrode materials have the advantage of structural designability, they have a large overpotential in zinc-ion batteries. Therefore, the charge storage capacity of photovoltaic-storage integrated batteries fabricated by coupling Zn / / nanosheet-organic electrode energy storage systems with solar cells needs further improvement. Summary of the Invention

[0003] To accelerate the storage rate of photogenerated charge from solar cells in zinc-ion batteries, this invention provides a method for preparing a nanosheet-organic active molecule-catalyst hybrid material with rapid charge storage rate and long cycle life, and its application in integrated photovoltaic-energy storage batteries. This method can reduce the overpotential of the energy storage electrode, improve the cycle life of zinc-ion batteries, and achieve the preparation of integrated photovoltaic-energy storage batteries with high overall conversion efficiency.

[0004] To achieve the above objectives, the technical solution of the present invention is as follows:

[0005] A method for preparing a nanosheet-organic active molecule-catalyst hybrid material, the method comprising the following steps:

[0006] (1) Mix nanomaterials and organic solvents, and peel off to obtain an organic dispersion of nanosheets;

[0007] (2) Add organic active molecules to the organic dispersion containing nanosheets to perform electrostatic self-assembly, so that the organic active molecules are intercalated into the nanosheets to obtain a nanosheet-organic molecule mixed dispersion.

[0008] (3) Add a crosslinking agent to the nanosheet-organic molecule mixed dispersion, and under the action of the first catalyst, the nanosheet and organic active molecules achieve covalent crosslinking. Then, the reaction products are separated to obtain nanosheet-organic electrode material.

[0009] (4) The nanosheet-organic electrode material is physically mixed with the second catalyst to obtain the nanosheet-organic active molecule-catalyst hybrid material; the second catalyst is a single-atom catalyst or a diatomic catalyst.

[0010] Optionally, the second catalyst comprises one or any combination of two single atoms selected from Ti single atoms, V single atoms, Mn single atoms, Fe single atoms, Co single atoms, Zn single atoms, Cu single atoms, Ni single atoms, Wo single atoms, Mo single atoms, Ru single atoms, Rh single atoms, Ir single atoms, Pd single atoms, Pt single atoms, Ag single atoms, and Au single atoms.

[0011] Optionally, in the diatomic catalyst, the first atom accounts for 0% to 100% of the total mass of the diatomic catalyst, and the second atom accounts for 0% to 100% of the total mass of the diatomic catalyst.

[0012] Optionally, in step (1), the nanosheet material includes one of MXene, graphene, black scale, graphynylene, transition metal sulfides, hexagonal boron nitride, graphitic carbon nitride, phosphorene, covalent organic frameworks and metal-organic frameworks, layered metal oxides, layered double hydroxides, layered metal carbides, metal nitrides and perovskites; the organic solvent includes one of ethylene glycol, glycerol, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, formamide, acetic acid, ethanol, methanol and N-methylpyrrolidone.

[0013] Optionally, in step (2), the organic active molecule includes one of sodium 4-aminoazobenzene-4-sulfonate, halogenated sulfide, 4,4'-dihydroxydiphenyl disulfide, 4,4'-diaminoazobenzene, thionine, 4-nitroazophenol, phenolic saffron, and aromatic nitro compounds; the aromatic nitro compounds are molecules containing a -OH aromatic ring, a -NH2 aromatic ring, an aromatic heterocycle, or an azo aromatic ring structure, and containing a -NO2 structure, including 4-nitrophenol, 3-nitrophenol, etc. The electrostatic self-assembly is one of 2-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol, 2-nitro-1-naphthol, 4-nitro-1-naphthol, 2,4-dinitronaphthol, 4-hydroxy-4-nitroazobenzene, 4-(4-nitrophenylazo)-1-naphthol, 1,8-dihydroxy-4,5-dinitroanthraquinone, 1-hydroxy-4-nitroanthraquinone, and 1-amino-4-nitroanthraquinone; the electrostatic self-assembly time is 10 min to 180 min.

[0014] Optionally, in step (3), the crosslinking agent includes one of dicarboxylic acids, acid anhydrides, dialdehydes, diisocyanates, and diacyl chlorides; the first catalyst includes one of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride / N-hydroxysuccinimide, triethylamine, and dibutyltin dilaurate; the temperature of the catalytic reaction is 0℃~120℃; the time of the catalytic reaction is 1h~12h; and the separation includes one or more of rotary evaporation, filtration washing, and centrifugal washing.

[0015] The present invention also discloses an integrated photovoltaic and energy storage battery, including a zinc-ion battery and a solar cell; the zinc-ion battery includes a positive electrode material, a zinc negative electrode material and an electrolyte; the positive electrode material is a nanosheet-organic active molecule-catalyst hybrid material prepared by the above preparation method.

[0016] Optionally, the method for preparing the integrated photovoltaic and energy storage battery includes the following steps:

[0017] (1) Using the nanosheet-organic active molecule-catalyst hybrid material as the positive electrode material, the positive electrode material is assembled with zinc negative electrode material and electrolyte to form a zinc-ion battery;

[0018] (2) Couple the zinc-ion battery with the solar cell to construct an integrated photovoltaic and energy storage battery.

[0019] Optionally, in step (1), the zinc negative electrode material includes zinc sheet and / or zinc powder; the electrolyte includes one of zinc sulfate electrolyte, zinc chloride electrolyte, zinc trifluoromethanesulfonate electrolyte, zinc perchlorate electrolyte, bis(trifluoromethanesulfonyl)imide zinc and zinc tetrafluoroborate; the concentration of the electrolyte is 0.0001 mol / L to 30 mol / L.

[0020] Optionally, in step (2), the solar cell includes one of perovskite solar cells, silicon solar cells, organic solar cells, nanocrystalline solar cells, CdTe solar cells, and CIGS solar cells.

[0021] Compared with existing methods, the present invention has the following advantages:

[0022] (1) This invention utilizes the covalent cross-linking of nanosheets with organic active molecules to increase the specific capacity of the electrode by increasing the redox active sites of the electrode; and for the first time, it applies single-atom catalysts or diatomic catalysts to the zinc-ion battery system, combining nanosheet-organic electrode materials with single-atom catalysts or diatomic catalysts to reduce the overpotential of the electrode, improve the storage rate of photogenerated charge and cycle life, and achieve a dual improvement in the charge storage rate and cycle life of zinc-ion batteries.

[0023] (2) The preparation method of the present invention is simple to operate and can be expanded to include more cathode material systems and catalysts.

[0024] (3) The method of the present invention is the first to couple solar cells with aqueous zinc-ion batteries to prepare an integrated photovoltaic and energy storage battery. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0026] Figure 1 This is a flowchart illustrating the preparation route of the MXene-organic-catalyst electrode in Example 1.

[0027] Figure 2 The constant current charge-discharge curves of the MXene-organic-catalyst electrode in Examples 1-3 and Comparative Example 1 are shown.

[0028] Figure 3 This is a schematic diagram of the photovoltaic-storage integrated battery in Example 1.

[0029] Figure 4 The cyclic charge-discharge curves are for different ratios in Examples 1 and 4-7. Detailed Implementation

[0030] To further understand the method of the present invention, preferred embodiments of the present invention are now provided, and detailed descriptions are given below with accompanying drawings.

[0031] Example 1

[0032] (1) The etched multilayer MXene was dispersed in N,N-dimethylformamide to prepare a dispersion with a mass fraction of 0.1wt%, and ultrasonicated for 2h to make it uniformly dispersed.

[0033] (2) Add 4-nitroazophenol to the dispersion obtained in step (1) and ultrasonically disperse for 30 min to allow 4-nitroazophenol to be intercalated into MXene nanosheets.

[0034] (3) Add crosslinking agent p-isophorone diisocyanate to the mixture obtained in step (2), and react at 80°C for 1 h under the catalysis of dibutyltin dilaurate. Centrifuge and wash the reaction product to obtain MXene-organic molecular hybrid material.

[0035] (4) Mix MXene-organic molecular hybrid material, Fe single atom, Co single atom, acetylene black and polyvinylidene fluoride, wherein the mass ratio of Fe single atom, Co single atom, acetylene black and polyvinylidene fluoride is 3:5:1:1, coat it on carbon cloth as positive electrode material, zinc sheet as negative electrode material, and 0.1mol / L zinc sulfate as electrolyte to assemble zinc-ion battery.

[0036] (5) Connect the positive and negative electrodes of the zinc-ion battery to FA x Cs1-x The anode and cathode of a PbI3 perovskite solar cell are connected to form an integrated photovoltaic and energy storage cell.

[0037] Example 2

[0038] The only difference between this embodiment and Embodiment 1 is that only Fe single atoms are used.

[0039] Example 3

[0040] The only difference between this embodiment and Embodiment 1 is that only Co single atoms are used.

[0041] Comparative Example 1

[0042] The only difference between this comparative example and Example 1 is that no Fe single atoms or Co single atoms are added.

[0043] Example 4

[0044] The only difference between this embodiment and Example 1 is that the mixing mass ratio of Fe single atoms, Co single atoms, acetylene black, and polyvinylidene fluoride is 4:4:1:1.

[0045] Example 5

[0046] The only difference between this embodiment and Example 1 is that the mixing mass ratio of Fe single atoms, Co single atoms, acetylene black, and polyvinylidene fluoride is 5:3:1:1.

[0047] Example 6

[0048] The only difference between this embodiment and Example 1 is that the mixing mass ratio of Fe single atoms, Co single atoms, acetylene black, and polyvinylidene fluoride is 6:2:1:1.

[0049] Example 7

[0050] The only difference between this embodiment and Example 1 is that the mixing mass ratio of Fe single atoms, Co single atoms, acetylene black, and polyvinylidene fluoride is 7:1:1:1.

[0051] Test case

[0052] 1. Cycle capacity tests were performed on the batteries prepared in Examples 1-3 and Comparative Example 1. The results are as follows: Figure 2 As shown.

[0053] 2. Cycle capacity tests were performed on the batteries prepared in Examples 1 and 4-7, and the results are as follows: Figure 4 As shown.

[0054] Example 8

[0055] The only difference between this embodiment and Example 1 is that the organic active molecule is phenolic saffron.

[0056] Example 9

[0057] The only difference between this embodiment and Example 1 is that the crosslinking agent is hexamethylene isocyanate.

[0058] Example 10

[0059] The only difference between this embodiment and Example 1 is that the catalyst in step (3) is dibutyltin dilaurate.

[0060] Example 11

[0061] The only difference between this embodiment and Example 1 is that the catalytic reaction temperature in step (3) is set to 50°C.

[0062] Example 12

[0063] The only difference between this embodiment and Example 1 is that in step (4), the catalyst is a Pt single-atom catalyst.

[0064] Example 13

[0065] The only difference between this embodiment and Embodiment 1 is that the negative electrode material is zinc powder.

[0066] Example 14

[0067] The only difference between this embodiment and Example 1 is that the electrolyte is 1 mol / L zinc tetrafluoroborate.

[0068] Example 15

[0069] The only difference between this embodiment and Embodiment 1 is that an organic solar cell is used to couple with a zinc-ion battery.

[0070] The effects of Examples 8-15 are the same as those of Example 1.

[0071] The above content provides a detailed description of the present invention. Any similar implementations made without departing from the method of the present invention should fall within the protection scope of the present invention.

Claims

1. A method for preparing an integrated photovoltaic and energy storage battery, characterized in that, The integrated photovoltaic and energy storage battery includes a zinc-ion battery and a solar cell; The zinc-ion battery includes a positive electrode material, a zinc negative electrode material, and an electrolyte; the positive electrode material is a nanosheet-organic active molecule-catalyst hybrid material. The method for preparing the integrated photovoltaic and energy storage battery includes the following steps: (a) Using the nanosheet-organic active molecule-catalyst hybrid material as the positive electrode material, the positive electrode material is assembled with zinc negative electrode material and electrolyte to form a zinc-ion battery; (b) Couple the zinc-ion battery with a solar cell to construct an integrated photovoltaic-storage battery; The preparation method of the nanosheet-organic active molecule-catalyst hybrid material includes the following steps: (1) Mix nanomaterials and organic solvents, and peel off to obtain an organic dispersion of nanosheets; (2) Add organic active molecules to the organic dispersion containing nanosheets to perform electrostatic self-assembly, so that the organic active molecules are intercalated into the nanosheets to obtain a nanosheet-organic molecule mixed dispersion. (3) Add a crosslinking agent to the nanosheet-organic molecule mixed dispersion, and under the action of the first catalyst, the nanosheet and organic active molecules achieve covalent crosslinking. Then, the reaction products are separated to obtain nanosheet-organic electrode material. (4) The nanosheet-organic electrode material is physically mixed with the second catalyst to obtain the nanosheet-organic active molecule-catalyst hybrid material; the second catalyst is a single-atom catalyst or a diatomic catalyst; The organic active molecules include one of 4,4'-diaminoazobenzene, thionine, 4-nitroazophenol, phenolic saffron, and aromatic nitro compounds; The second catalyst includes one or any combination of two single atoms selected from Ti single atoms, V single atoms, Fe single atoms, Co single atoms, Zn single atoms, Cu single atoms, Ni single atoms, Wo single atoms, Mo single atoms, Ru single atoms, Rh single atoms, Ir single atoms, Pd single atoms, Pt single atoms, Ag single atoms, and Au single atoms.

2. The method for preparing the integrated photovoltaic and energy storage battery according to claim 1, characterized in that, In the diatomic catalyst, the first atom accounts for 0% to 100% of the total mass of the diatomic catalyst, and the second atom accounts for 0% to 100% of the total mass of the diatomic catalyst.

3. The method for preparing the integrated photovoltaic and energy storage battery according to claim 1, characterized in that, In step (1), the nanosheet material includes one of MXene, graphene, black scale, graphynylene, transition metal sulfide, hexagonal boron nitride, graphitic carbon nitride, phosphorene, covalent organic framework and metal-organic framework, layered metal oxide, layered double hydroxide, layered metal carbide, metal nitride and perovskite. The organic solvent includes one of ethylene glycol, glycerol, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, formamide, acetic acid, ethanol, methanol, and N-methylpyrrolidone.

4. The method for preparing the integrated photovoltaic and energy storage battery according to claim 1, characterized in that, In step (2), the aromatic nitro compound is a molecule containing a -OH aromatic ring, a -NH2 aromatic ring, an aromatic heterocyclic ring, or an azo aromatic ring structure, and containing a -NO2 structure, including one of 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol, 2-nitro-1-naphthol, 4-nitro-1-naphthol, 2,4-dinitronaphthol, 4-hydroxy-4-nitroazobenzene, 4-(4-nitrophenylazo)-1-naphthol, 1,8-dihydroxy-4,5-dinitroanthraquinone, 1-hydroxy-4-nitroanthraquinone, and 1-amino-4-nitroanthraquinone; The electrostatic self-assembly time is 10 min to 180 min.

5. The method for preparing the integrated photovoltaic and energy storage battery according to claim 1, characterized in that, In step (3), the crosslinking agent includes one of the following organic molecules: dicarboxylic acid, acid anhydride, dialdehyde, diisocyanate, and diacyl chloride; The first catalyst comprises one of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride / N-hydroxysuccinimide, triethylamine, and dibutyltin dilaurate; The temperature for the catalytic reaction is 0℃~120℃; the reaction time is 1h~12h. The separation includes one or more of the following: rotary evaporation, filtration washing, and centrifugal washing.

6. The method for preparing the integrated photovoltaic and energy storage battery according to claim 1, characterized in that, In step (a), the zinc anode material includes zinc sheets and / or zinc powder; The electrolyte includes one of zinc sulfate electrolyte, zinc chloride electrolyte, zinc trifluoromethanesulfonate electrolyte, zinc perchlorate electrolyte, bis(trifluoromethanesulfonyl)imide zinc, and zinc tetrafluoroborate. The concentration of the electrolyte is 0.0001 mol / L to 30 mol / L.

7. The method for preparing the integrated photovoltaic and energy storage battery according to claim 1, characterized in that, In step (b), the solar cell includes one of perovskite solar cells, silicon solar cells, organic solar cells, nanocrystalline solar cells, CdTe solar cells, and CIGS solar cells.

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