Zn-I2 battery electrolyte and preparation method and application thereof

Abstract

The invention discloses Zn-I2 battery electrolyte as well as a preparation method and application thereof. The Zn-I2 battery electrolyte comprises an additive, zinc salt and a composite solvent, the additive contains halogen groups and polar functional groups; the halogen group is selected from one or more than two of F, Cl and Br. Through halogen groups in the additive, the iodine negative ion intermediate is effectively stabilized, so that a Zn-I2 battery is subjected to multi-electron transfer, and the specific capacity of the photoelectric storage integrated battery is improved; the polar functional groups in the additive can homogenize the electric field distribution on the Zn surface, reduce the nucleation overpotential corrosion current and hydrogen evolution current of Zn, change the diffusion path of Zn < 2 + > on an anode interface and improve the cycle stability of the Zn-I2 battery, the Zn-I2 battery with high specific capacity and long cycle life can be obtained by matching the two functional groups, and the Zn-I2 battery is coupled with a solar battery, so that the service life of the Zn-I2 battery is prolonged. Therefore, the overall conversion efficiency and the service life of the photoelectric storage integrated battery are improved.

Description

Technical Field

[0001] The present invention relates to the field of self-powered technology, and in particular to a Zn-I2 battery electrolyte and a preparation method and application thereof. Background Art

[0002] As the global demand for renewable energy increases, the development of efficient and low-cost self-powered technologies has become increasingly important. Photovoltaic storage batteries based on Zn-I2 cells can generate electricity during the day while storing electricity for use at night or on cloudy days, thereby improving the overall efficiency and stability of the system. However, the two-electron reaction of Zn-I2 currently makes its specific capacity unable to meet the requirements of practical applications. In addition, due to the shuttle effect of multiple iodide ions, the corrosion reaction of the zinc negative electrode is accelerated, reducing its cycle life. Summary of the invention

[0003] The purpose of the present invention is to overcome the above-mentioned defects of the prior art and to provide a Zn-I2 battery electrolyte and a preparation method and application thereof that can effectively improve the specific capacity and cycle life of a photovoltaic storage integrated battery.

[0004] In order to achieve the above object, the technical solution of the present invention is as follows:

[0005] A Zn-I2 battery electrolyte comprises an additive, a zinc salt and a composite solvent; the additive contains a halogen group and a polar functional group; the halogen group is selected from one or more of F, Cl and Br; the polar functional group is selected from one or more of alcohol, carbonyl, quinone, carboxylic acid, amide, primary amine, secondary amine, imine, imide, azo, hydrazine, hydrazide, cyanate, -C≡N, isonitrile, isocyanate, nitrate, nitrite, -NO2, pyridine, pyrrole, phosphate diester, phosphite, phosphate, thioether, sulfone, sulfoxide, sulfonic acid, thiocyanate, -SO4 and thiol.

[0006] Optionally, the mass percentage of the polar functional group in the additive is 0% to 90%; the mass percentage of the halogen group in the additive is 0% to 90%.

[0007] Optionally, the additive includes 2-bromoethanol, 3-bromopropionic acid, 2-bromoethylamine, 4-bromophenol, 2,3-dibromo-1-propanol, 3,4-dibromobenzoic acid, 2,2-dibromoethylamine, 2,4,6-tribromophenol, 2,3,4,6-tetrabromo-D-glucose, 2,4,6-tribromophenol, 1,2,3-tribromo-2-propanol, 2,3,4-tribromo-D-glucose, 2,3,4,5-tetrabromophenol, 2,3,4,5,6-pentabromobenzene. Acid, 2-bromobenzoic acid, 3-bromobenzoic acid, 4-bromobenzoic acid, 2,3-dibromobenzoic acid, 2,4-dibromobenzoic acid, 2,5-dibromobenzoic acid, 2,6-dibromobenzoic acid, 2,3,4-tribromobenzoic acid, 2,3,5-tribromobenzoic acid, 2,3,6-tribromobenzoic acid, 2,4,6-tribromobenzoic acid, 2,3,4,5,6-pentabromobenzenesulfonic acid, 2-bromobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 4-bromobenzenesulfonic acid, 2,3-dibromobenzenesulfonic acid, 2,4- Dibromobenzenesulfonic acid, 2,5-dibromobenzenesulfonic acid, 2,6-dibromobenzenesulfonic acid, 2,3,4-tribromobenzenesulfonic acid, 2,3,5-tribromobenzenesulfonic acid, 2,3,6-tribromobenzenesulfonic acid, 2,4,6-tribromobenzenesulfonic acid, 1-amino-4-bromoanthraquinone-2-sulfonate sodium, anthraquinone-1-sulfonate sodium, anthraquinone-2-sulfonate sodium, 1-aminoanthraquinone, 1-bromoanthraquinone, 2-bromoanthraquinone, 1-hydroxyanthraquinone, 1,4-difluoroanthraquinone, 1-hydroxy-4-nitroanthraquinone, 1,4,5 ,8-tetrachloroanthraquinone, 1,4-dichloroanthraquinone, 1,8-dichloroanthraquinone, 1,5-dichloroanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, sodium 4-bromobenzenesulfinate, sodium 2-bromoethylsulfonate, 1-chloroanthraquinone, 1,5-dibromoanthraquinone, 1-amino-4-bromo-2-methylanthraquinone qulinone, 1-nitroanthraquinone, 1-amino-4-hydroxyanthraquinone, 2,6-dibromoanthraquinone, 2-chloroanthraquinone, 1-amino-2,4-dibromoanthraquinone, one or more thereof.

[0008] Optionally, in the Zn-I2 battery electrolyte, the concentration of the additive is 0.000001 mol / L to 10 mol / L.

[0009] Optionally, the zinc salt includes one of zinc sulfate, zinc chloride, zinc trifluoromethanesulfonate, zinc perchlorate, zinc bis(trifluoromethanesulfonyl)imide and zinc tetrafluoroborate.

[0010] Optionally, in the Zn-I2 battery electrolyte, the concentration of zinc salt is 0.001 mol / L to 50 mol / L.

[0011] Optionally, the composite solvent includes an organic solvent and water.

[0012] Optionally, the organic solvent includes one of ethylene glycol, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, polyethylene glycol, propylene glycol, succinonitrile, liquid surfactant, diethylene glycol dimethyl ether, carbonate, diethylene glycol, butyrolactam, cyclopentane sulfone, ethylene glycol monomethyl ether, dimethyl methylphosphonate, N,N-dimethylformamide, polyethylene glycol diacid, diethylene glycol monoethyl ether, N,N-dimethyltrifluoroacetamide and tributyl phosphate.

[0013] Optionally, in the composite solvent, the organic solvent accounts for 0wt% to 100wt% of the mass of water.

[0014] The present invention also discloses a method for preparing the Zn-I2 battery electrolyte as described above, comprising the following steps: mixing an additive, a zinc salt and a composite solvent to obtain the Zn-I2 battery electrolyte.

[0015] The present invention also discloses a photovoltaic and energy storage integrated battery, which comprises a Zn-I2 battery and a solar cell; the Zn-I2 battery comprises a positive electrode, a zinc negative electrode, a diaphragm and the above-mentioned Zn-I2 battery electrolyte; the solar cell comprises one of a perovskite solar cell, a silicon solar cell, an organic solar cell, a nanocrystalline solar cell, a CdTe solar cell and a CIGS solar cell.

[0016] Optionally, the positive electrode includes a positive electrode current collector and a positive electrode active material coated on the positive electrode current collector.

[0017] Optionally, the positive electrode current collector includes carbon paper, titanium foil, titanium mesh, carbon cloth, porous carbon, single-atom or double-atom catalyst or porous metal current collector; the positive electrode active material is iodine; and the zinc negative electrode includes zinc sheet, zinc powder or zinc film.

[0018] Optionally, the thickness of the zinc sheet and the zinc film is 1 nm to 1 cm respectively; the particle size of the zinc powder is 0.1 nm to 10 cm.

[0019] Optionally, the membrane includes one of a glass fiber membrane, a cellulose-based membrane, a polyacrylonitrile-based membrane, a Nafion-based membrane, a graphene-based membrane, a polyolefin composite membrane, a glass fiber filter paper-type membrane, an organic polymer non-woven fabric-type membrane, a woven membrane, a non-woven membrane, a composite membrane, an ion exchange membrane and a gel electrolyte.

[0020] Optionally, the method for preparing the photovoltaic and energy storage integrated battery comprises the following steps:

[0021] (1) Assembling the Zn-I2 battery electrolyte with a zinc negative electrode, a separator and a positive electrode to obtain a Zn-I2 battery;

[0022] (2) The Zn-I2 battery is coupled with a solar cell to obtain the photovoltaic and energy storage integrated battery.

[0023] Compared with the existing method, the present invention has the following beneficial effects:

[0024] (1) In order to activate the occurrence of the high-valent iodine reaction, the present invention dopes the electrolyte with organic molecules containing -F, -Cl or -Br. These halogen groups can stabilize the iodine ion intermediate and make it change to a higher valence state. In addition, the additive also contains polar groups, so that the additive is adsorbed on the zinc anode interface during the charge and discharge process, which homogenizes the electric field distribution on the Zn surface, reduces the nucleation overpotential corrosion current and hydrogen evolution current of Zn, and changes the Zn 2+ The diffusion path at the anode interface improves the cycle stability of the battery. The combination of the two functional groups produces a Zn-I2 battery with high specific capacity and long cycle life, and coupled with a solar cell, improves the overall conversion efficiency and service life of the light-charged Zn-I2 battery.

[0025] (2) The method of the present invention couples a solar cell with a Zn-I2 cell for the first time to prepare a photovoltaic and energy storage integrated cell.

[0026] (3) The preparation cost of the present invention is low and has great industrial potential. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0028] Figure 1 Schematic diagram of the button-type Zn-I2 battery in Example 1.

[0029] Figure 2 Schematic diagram of the liquid flow type Zn-I2 battery in Example 8.

[0030] Figure 3 1 and 2 are the Zn / / Zn symmetric battery cycle curves of Example 1 and Comparative Example 1.

[0031] Figure 4 The cyclic charge and discharge curves of the Zn / / I2 batteries of Example 1, Example 2 and Example 3 are shown. DETAILED DESCRIPTION

[0032] In order to further understand the method of the present invention, a preferred embodiment of the present invention is now given and described in detail with the accompanying drawings as follows.

[0033] Example 1

[0034] The Zn-I2 battery electrolyte of this embodiment includes 0.1 mol / L 4-bromobenzenesulfonic acid additive, 1 mol / L zinc sulfate and a composite solvent, wherein the composite solvent is a mixture of N,N-dimethylformamide and water.

[0035] The method for preparing a photovoltaic and energy storage integrated battery of this embodiment comprises the following steps:

[0036] (1) Preparation of Zn-I2 battery electrolyte: The above-mentioned 4-bromobenzenesulfonic acid additive, zinc sulfate and composite solvent are mixed, and the mass fraction of the organic solvent relative to water is 50wt%.

[0037] (2) Preparation of zinc negative electrode: Zinc powder (0.01 mm), acetylene black and polyvinylidene fluoride were mixed in a mass ratio of 7:2:1, N-methylpyrrolidone was added thereto, the mixture was mixed into a viscous state, and the mixture was coated on carbon paper and dried.

[0038] (3) Select a glass fiber diaphragm with a thickness of 1 mm.

[0039] (4) Preparation of positive electrode: Mix activated carbon and iodine in a mass ratio of 1:1, place it in a high-pressure reactor at 90°C for 3 hours. Mix iodine, acetylene black and polyvinylidene fluoride loaded on activated carbon in a mass ratio of 8:1:1, add N-methylpyrrolidone, mix until it becomes viscous, and coat it on carbon paper to dry.

[0040] (5) Add electrolyte to the diaphragm and assemble it with the zinc negative electrode and positive electrode to form Figure 1 Button-type Zn-I2 battery shown.

[0041] (6) Connect the positive and negative electrodes of the Zn-I2 battery to the anode and cathode of the perovskite solar cell to construct a photovoltaic and energy storage integrated battery.

[0042] Comparative Example 1

[0043] The only difference between this comparative example and Example 1 is that no additive is added to the electrolyte.

[0044] Example 2

[0045] The only difference between this embodiment and embodiment 1 is that the additive is benzenesulfonic acid.

[0046] Example 3

[0047] The difference between this embodiment and embodiment 1 is that the additive is bromobenzene.

[0048] Test Example: The performance of the batteries prepared in the examples and comparative examples was tested. The results are as follows: Figure 3-4 shown.

[0049] Example 4

[0050] The difference between this embodiment and embodiment 1 is that zinc sulfate is replaced by zinc tetrafluoroborate.

[0051] Example 5

[0052] The only difference between this embodiment and embodiment 1 is that the zinc powder is replaced with a zinc sheet with a thickness of 0.05 mm.

[0053] Example 6

[0054] The only difference between this embodiment and embodiment 1 is that the glass fiber separator is replaced with a gel electrolyte.

[0055] Example 7

[0056] The only difference between this embodiment and embodiment 1 is that the activated carbon mixed with iodine is replaced by a ZIF-8 catalyst loaded with Fe single atoms mixed with iodine.

[0057] Example 8

[0058] The difference between this embodiment and embodiment 1 is that the button-type battery is replaced with a flow battery, and the structure is as follows: Figure 2 shown.

[0059] Example 9

[0060] The only difference between this embodiment and Embodiment 1 is that the perovskite solar cell is replaced with a crystalline silicon solar cell.

[0061] Example 10

[0062] The preparation method is similar to that of Example 1, except that the solar cell and the Zn-I2 battery external circuit connection method are integrated into one.

[0063] The effects of Examples 2 to 10 are the same as those of Example 1.

[0064] It should be noted that, in addition to the 4-bromobenzenesulfonic acid additive, benzenesulfonic acid and bromobenzene used in the embodiments of the present application, any compound that can simultaneously provide F, Cl or Br halogen groups and alcohol, carbonyl, quinone, carboxylic acid, amide, primary amine, secondary amine, imine, imide, azo, hydrazine, hydrazide, cyanate, -C≡N, isonitrile, isocyanate, nitrate, nitrite, -NO2, pyridine, pyrrole, phosphate diester, phosphite, phosphate, sulfide, sulfone, sulfoxide, sulfonic acid, thiocyanate, -SO4 or thiol polar functional groups can be applied to the present application and have similar functions and effects to the embodiments of the present application. For example, the additives include 2-bromoethanol, 3-bromopropionic acid, 2-bromoethylamine, 4-bromophenol, 2,3-dibromo-1-propanol, 3,4-dibromobenzoic acid, 2,2-dibromoethylamine, 2,4,6-tribromophenol, 2,3,4,6-tetrabromo-D-glucose, 2,4,6-tribromophenol, 1,2,3-tribromo-2-propanol, 2,3,4-tribromo-D-glucose, 2,3,4,5-tetrabromophenol, 2,3,4,5,6-pentabromobenzoic acid. , 2-bromobenzoic acid, 3-bromobenzoic acid, 4-bromobenzoic acid, 2,3-dibromobenzoic acid, 2,4-dibromobenzoic acid, 2,5-dibromobenzoic acid, 2,6-dibromobenzoic acid, 2,3,4-tribromobenzoic acid, 2,3,5-tribromobenzoic acid, 2,3,6-tribromobenzoic acid, 2,4,6-tribromobenzoic acid, 2,3,4,5,6-pentabromobenzenesulfonic acid, 2-bromobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2,3-dibromobenzenesulfonic acid, 2,4-dibromobenzenesulfonic acid , 2,5-dibromobenzenesulfonic acid, 2,6-dibromobenzenesulfonic acid, 2,3,4-tribromobenzenesulfonic acid, 2,3,5-tribromobenzenesulfonic acid, 2,3,6-tribromobenzenesulfonic acid, 2,4,6-tribromobenzenesulfonic acid, 1-amino-4-bromoanthraquinone-2-sulfonate sodium, anthraquinone-1-sulfonate sodium, anthraquinone-2-sulfonate sodium, 1-aminoanthraquinone, 1-bromoanthraquinone, 2-bromoanthraquinone, 1-hydroxyanthraquinone, 1,4-difluoroanthraquinone, 1-hydroxy-4-nitroanthraquinone, 1,4,5,8- One or more of tetrachloroanthraquinone, 1,4-dichloroanthraquinone, 1,8-dichloroanthraquinone, 1,5-dichloroanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, sodium 4-bromobenzenesulfinate, sodium 2-bromoethylsulfonate, 1-chloroanthraquinone, 1,5-dibromoanthraquinone, 1-amino-4-bromo-2-methylanthraquinone, 1-nitroanthraquinone, 1-amino-4-hydroxyanthraquinone, 2,6-dibromoanthraquinone, 2-chloroanthraquinone, and 1-amino-2,4-dibromoanthraquinone.

[0065] The above content is a detailed description of the present invention. Similar implementations made without departing from the method of the present invention should all fall within the protection scope of the present invention.

Claims

1. A Zn-I2 battery electrolyte, characterized in that: Includes additives, zinc salts and co-solvents; The additive contains a halogen group and a polar functional group; The halogen group is selected from one or more of F, Cl and Br; The polar functional group is selected from one or more of alcohol, carbonyl, quinone, carboxylic acid, amide, primary amine, secondary amine, imine, imide, azo, hydrazine, hydrazide, cyanate, -C≡N, isonitrile, isocyanate, nitrate, nitrite, -NO2, pyridine, pyrrole, phosphodiester, phosphite, phosphate, thioether, sulfone, sulfoxide, sulfonic acid, thiocyanate, -SO4 and thiol.

2. The Zn-I2 battery electrolyte according to claim 1, characterized in that: The mass percentage of the polar functional group in the additive is 0% to 90%; The mass percentage of the halogen group in the additive is 0% to 90%.

3. The Zn-I2 battery electrolyte according to claim 1, characterized in that: The additives include 2-bromoethanol, 3-bromopropionic acid, 2-bromoethylamine, 4-bromophenol, 2,3-dibromo-1-propanol, 3,4-dibromobenzoic acid, 2,2-dibromoethylamine, 2,4,6-tribromophenol, 2,3,4,6-tetrabromo-D-glucose, 2,4,6-tribromophenol, 1,2,3-tribromo-2-propanol, 2,3,4-tribromo-D-glucose, 2,3,4,5-tetrabromophenol, 2,3,4,5,6-pentabromobenzoic acid, 2 -bromobenzoic acid, 3-bromobenzoic acid, 4-bromobenzoic acid, 2,3-dibromobenzoic acid, 2,4-dibromobenzoic acid, 2,5-dibromobenzoic acid, 2,6-dibromobenzoic acid, 2,3,4-tribromobenzoic acid, 2,3,5-tribromobenzoic acid, 2,3,6-tribromobenzoic acid, 2,4,6-tribromobenzoic acid, 2,3,4,5,6-pentabromobenzenesulfonic acid, 2-bromobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 4-bromobenzenesulfonic acid, 2,3-dibromobenzenesulfonic acid, 2,4-dibromo Benzenesulfonic acid, 2,5-dibromobenzenesulfonic acid, 2,6-dibromobenzenesulfonic acid, 2,3,4-tribromobenzenesulfonic acid, 2,3,5-tribromobenzenesulfonic acid, 2,3,6-tribromobenzenesulfonic acid, 2,4,6-tribromobenzenesulfonic acid, 1-amino-4-bromoanthraquinone-2-sulfonate sodium, anthraquinone-1-sulfonate sodium, anthraquinone-2-sulfonate sodium, 1-aminoanthraquinone, 1-bromoanthraquinone, 2-bromoanthraquinone, 1-hydroxyanthraquinone, 1,4-difluoroanthraquinone, 1-hydroxy-4-nitroanthraquinone, 1,4,5, One or more of 8-tetrachloroanthraquinone, 1,4-dichloroanthraquinone, 1,8-dichloroanthraquinone, 1,5-dichloroanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, sodium 4-bromobenzenesulfinate, sodium 2-bromoethylsulfonate, 1-chloroanthraquinone, 1,5-dibromoanthraquinone, 1-amino-4-bromo-2-methylanthraquinone, 1-nitroanthraquinone, 1-amino-4-hydroxyanthraquinone, 2,6-dibromoanthraquinone, 2-chloroanthraquinone and 1-amino-2,4-dibromoanthraquinone.

4. The Zn-I2 battery electrolyte according to claim 1, characterized in that: In the Zn-I2 battery electrolyte, the concentration of the additive is 0.000001 mol / L to 10 mol / L.

5. The Zn-I2 battery electrolyte according to claim 1, characterized in that: The zinc salt includes one of zinc sulfate, zinc chloride, zinc trifluoromethanesulfonate, zinc perchlorate, bis(trifluoromethanesulfonyl)imide zinc and zinc tetrafluoroborate; In the Zn-I2 battery electrolyte, the concentration of zinc salt is 0.001 mol / L to 50 mol / L.

6. The Zn-I2 battery electrolyte according to claim 1, characterized in that: The composite solvent comprises an organic solvent and water; The organic solvent comprises one of ethylene glycol, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, polyethylene glycol, glycerol, succinonitrile, liquid surfactant, diethylene glycol dimethyl ether, carbonate, diethylene glycol, butyrolactam, cyclopentane, ethylene glycol monomethyl ether, dimethyl methylphosphonate, N,N-dimethylformamide, polyethylene glycol diacid, diethylene glycol monoethyl ether, N,N-dimethyltrifluoroacetamide and tributyl phosphate; In the composite solvent, the organic solvent accounts for 0wt% to 100wt% of the mass of water.

7. A method for preparing a Zn-I2 battery electrolyte as claimed in any one of claims 1 to 6, characterized in that: The following steps are involved: The additive, the zinc salt and the composite solvent are mixed to obtain the Zn-I2 battery electrolyte.

8. A photovoltaic and energy storage integrated battery, characterized in that: The photovoltaic storage integrated battery comprises a Zn-I2 battery and a solar cell; The Zn-I2 battery comprises a positive electrode, a zinc negative electrode, a separator and a Zn-I2 battery electrolyte according to any one of claims 1 to 6; The solar cell includes one of a perovskite solar cell, a silicon solar cell, an organic solar cell, a nanocrystalline solar cell, a CdTe solar cell and a CIGS solar cell.

9. The photovoltaic and energy storage integrated battery according to claim 8, characterized in that: The positive electrode comprises a positive electrode current collector and a positive electrode active material coated on the positive electrode current collector; The positive electrode current collector includes carbon paper, titanium foil, titanium mesh, carbon cloth, porous carbon, single-atom or double-atom catalyst or porous metal current collector; The positive electrode active material is iodine; The zinc negative electrode comprises a zinc sheet, zinc powder or a zinc film; The thickness of the zinc sheet and the zinc film are 1 nm to 1 cm respectively; The particle size of the zinc powder is 0.1nm to 10cm; The diaphragm includes one of a glass fiber diaphragm, a cellulose-based membrane, a polyacrylonitrile-based membrane, a Nafion-based membrane, a graphene-based membrane, a polyolefin composite diaphragm, a glass fiber filter paper-type diaphragm, an organic polymer non-woven fabric-type diaphragm, a woven membrane, a non-woven membrane, a composite membrane, an ion exchange membrane and a gel electrolyte.

10. The photovoltaic and energy storage integrated battery according to claim 8, characterized in that: The preparation method of the photovoltaic and energy storage integrated battery comprises the following steps: (1) Assembling the Zn-I2 battery electrolyte with a zinc negative electrode, a separator and a positive electrode to obtain a Zn-I2 battery; (2) The Zn-I2 battery is coupled with a solar cell to obtain the photovoltaic and energy storage integrated battery.

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