CN114899347B - Application of surfactant-embedded multi-metal oxygen cluster compound in zinc electrode protection, zinc-based composite pole piece, preparation method and application - Google Patents
Application of surfactant-embedded multi-metal oxygen cluster compound in zinc electrode protection, zinc-based composite pole piece, preparation method and application Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 188
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 94
- 239000002184 metal Substances 0.000 title claims abstract description 86
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 86
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 78
- 239000001301 oxygen Substances 0.000 title claims abstract description 78
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 150000001875 compounds Chemical class 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 26
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- 150000001450 anions Chemical class 0.000 claims description 4
- PSLWZOIUBRXAQW-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC PSLWZOIUBRXAQW-UHFFFAOYSA-M 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 3
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical compound [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 7
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 66
- 239000000243 solution Substances 0.000 description 29
- 101150034825 DODA gene Proteins 0.000 description 27
- 235000005583 doda Nutrition 0.000 description 27
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 27
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- 230000009286 beneficial effect Effects 0.000 description 4
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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Abstract
The invention provides an application of a surfactant-embedded multi-metal oxygen cluster compound in zinc electrode protection, a zinc-based composite pole piece, a preparation method and an application thereof, and belongs to the technical field of functional materials. According to the invention, the multi-metal oxygen cluster compound and the cationic surfactant are compounded through electrostatic action, the obtained surfactant embedded multi-metal oxygen cluster compound (SEP) can be self-assembled at a water-air interface to form a uniform SEP film, the SEP film is an amphiphilic film, has atom size uniformity and controllable thickness, can meet nanoscale size requirements, is convenient to transfer the SEP film to the surface of a metal zinc sheet through LB film technology to modify the metal zinc sheet, and the obtained zinc-based composite pole sheet serving as a negative electrode is used in a water-based zinc ion battery, so that zinc ion transmission kinetics can be accelerated; and the SEP combines the rigidity of inorganic materials and the flexibility of organic materials, has good chemical stability, and can still exist stably in long-time electrochemical circulation.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to application of a surfactant embedded multi-metal oxygen cluster compound in zinc electrode protection, a zinc-based composite pole piece, a preparation method and application.
Background
Aqueous zinc ion battery systems are of great interest due to their high safety, low cost, non-toxicity and relatively high theoretical specific capacity. However, the aqueous zinc ion battery has poor cycle reversibility, and dendrite growth caused by uneven zinc ion deposition is one of the causes of the problem, which limits the further development of the aqueous zinc ion battery.
By constructing a Solid Electrolyte Interface (SEI) between the zinc metal anode and the electrolyte, uniform deposition of zinc ions is induced, dendrite growth can be avoided, and simultaneously corrosion of the electrolyte to the zinc metal anode can be effectively isolated. At present, materials for constructing SEI comprise organic materials, inorganic materials or organic-inorganic hybrid materials, wherein the organic materials have flexible characteristics but poor mechanical strength, and the structure is easy to collapse under the condition of high deposition specific capacity; inorganic materials have strong rigidity, but are difficult to maintain structural integrity under high current density, rapid charge and discharge conditions. Therefore, the combination of the organic material and the inorganic material is expected to realize the long-cycle stability of the battery under the conditions of high deposition specific capacity and high current density. The organic-inorganic composite SEI layer constructed by the prior art is uneven in thickness and is generally thicker, and the uneven deposition of zinc ions on the surface of an electrode and the slow migration dynamics of the zinc ions are easy to cause (Angew.chem. 2020,132,16737-16744).
Disclosure of Invention
The invention aims to provide application of a surfactant-embedded multi-metal oxygen cluster compound in zinc electrode protection, a zinc-based composite pole piece, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides application of a surfactant-embedded multi-metal oxygen cluster compound in zinc electrode protection, wherein the surfactant-embedded multi-metal oxygen cluster compound comprises inorganic groups and organic groups which are combined through electrostatic action, the raw material for providing the inorganic groups is a multi-metal oxygen cluster compound, and the raw material for providing the organic groups is a cationic surfactant.
Preferably, the anions of the multi-metallic oxygen cluster compound comprise [ PW 12 O 40 ] 3- 、[SiW 12 O 40 ] 4- Or [ P ] 2 W 18 O 62 ] 6- Counter ions include H + 、Na + Or K + 。
Preferably, the cationic surfactant comprises dioctadecyl dimethyl ammonium bromide, tetraheptyl ammonium bromide, cetyl trimethyl ammonium bromide or dodecyl trimethyl ammonium bromide.
Preferably, the molar ratio of the organic groups to the inorganic groups is (3-6): 1.
preferably, the zinc electrode is a negative electrode of an aqueous zinc ion battery.
The invention provides a zinc-based composite pole piece, which comprises a metal zinc sheet and an organic-inorganic hybridization modification layer modified on one side of the metal zinc sheet, wherein the organic-inorganic hybridization modification layer is made of a surfactant embedded multi-metal oxygen cluster compound.
Preferably, the thickness of the organic-inorganic hybridization modification layer is 4-24 nm.
The invention provides a preparation method of the zinc-based composite pole piece, which comprises the following steps:
mixing the surfactant-embedded multi-metal oxygen cluster compound with an organic solvent to obtain a surfactant-embedded multi-metal oxygen cluster compound solution;
the surfactant-embedded multi-metal oxygen cluster compound solution is dripped on the water surface, and a film is formed on the water surface, so that the surfactant-embedded multi-metal oxygen cluster compound film is obtained;
and transferring the surfactant-embedded multi-metal oxygen cluster composite film to one side of a metal zinc sheet, and drying to form an organic-inorganic hybridization modification layer on one side of the metal zinc sheet to obtain the zinc-based composite pole piece.
Preferably, the concentration of the surfactant-embedded multi-metal oxygen cluster composite solution is 1.5-2 mmol/L, and the dropping rate of the surfactant-embedded multi-metal oxygen cluster composite solution is 1-4 mu L/s.
The invention provides an application of the zinc-based composite pole piece prepared by the technical scheme or the preparation method of the technical scheme as a negative electrode of a water-based zinc ion battery.
The invention provides application of a surfactant-embedded multi-metal oxygen cluster compound in zinc electrode protection, wherein the surfactant-embedded multi-metal oxygen cluster compound comprises inorganic groups and organic groups which are combined through electrostatic action, the raw material for providing the inorganic groups is a multi-metal oxygen cluster compound, and the raw material for providing the organic groups is a cationic surfactant. According to the invention, the multi-metal oxygen cluster compound and the cationic surfactant are compounded through electrostatic action, the obtained surfactant is embedded into the multi-metal oxygen cluster compound (SEP) and can be self-assembled at a water-air interface to form a uniform SEP film, the SEP film is an amphiphilic film and has uniformity of atomic size, the thickness is controllable, the nano-scale size requirement can be met, the multi-metal oxygen cluster compound is conveniently transferred to the surface of a metal zinc sheet through LB film technology to modify the metal zinc sheet, the obtained zinc-based composite pole piece (SEP/Zn) is used as a negative electrode in a water-based zinc ion battery, the ultra-thin thickness of the SEP film and the uniform arrangement of SEP molecules are beneficial to accelerating zinc ion transmission kinetics, and the functions of the multi-metal oxygen cluster compound and the cationic surfactant in the SEP film cooperate to realize uniform deposition of zinc ions, effectively inhibit dendrites, so that the cycle reversibility is realized; in addition, the SEP combines the rigidity of inorganic materials and the flexibility of organic materials, has good chemical stability, and can still exist stably in long-time electrochemical circulation.
Drawings
FIG. 1 is an SEM image of the SEP film prepared in example 1 on a zinc sheet and a corresponding EDS mapping image;
FIG. 2 is an AFM image of the SEP film prepared in example 1;
FIG. 3 is a symmetrical battery SEP/Zn and Zn DODA/Zn and Zn DODA/Zn based on SEP/Zn assembly in example 1 4 SiW 12 O 40 /Zn||Zn 4 SiW 12 O 40 Cycle life comparison chart of Zn under the condition of high current density;
FIG. 4 is a graph of the cycle life of a symmetric battery SEP/Zn under high current density conditions based on the SEP/Zn assembly of example 2;
FIG. 5 is a graph comparing coulombic efficiencies of half-cell Zn SEP/Cu and Zn Cu under low current density conditions;
FIG. 6 is a Scanning Electron Microscope (SEM) image of a bare Zn cathode after 600 cycles of Zn of a symmetric battery under high current density;
FIG. 7 is a Scanning Electron Microscope (SEM) image of the SEP/Zn negative electrode of a symmetric battery assembled based on SEP/Zn of example 1 after 600 cycles of SEP/Zn under high current density conditions;
FIG. 8 is a graph comparing corrosion curves of bare Zn cathodes in a symmetric battery Zn|| Zn and SEP/Zn cathodes in a symmetric battery SEP/Zn| SEP/Zn assembled based on SEP/Zn in example 1;
FIG. 9 is a SEP/Zn symmetric battery at 10mA/cm based on SEP/Zn assembly in example 1 2 XPS graph at the end of charging after cycling.
Detailed Description
The invention provides application of a surfactant-embedded multi-metal oxygen cluster compound in zinc electrode protection, wherein the surfactant-embedded multi-metal oxygen cluster compound comprises inorganic groups and organic groups which are combined through electrostatic action, the raw material for providing the inorganic groups is a multi-metal oxygen cluster compound, and the raw material for providing the organic groups is a cationic surfactant.
In the present invention, the zinc electrode is preferably a negative electrode of an aqueous zinc ion battery.
In the present invention, the anions of the multi-metallic oxygen cluster compound preferably include [ PW 12 O 40 ] 3- 、 [SiW 12 O 40 ] 4- Or [ P ] 2 W 18 O 62 ] 6- The counter ion preferably comprises H + 、Na + Or K + 。
In the present invention, the cationic surfactant preferably includes dioctadecyl dimethyl ammonium bromide (C 38 H 80 NBr), tetraheptyl ammonium bromide (C) 28 H 60 NBr), cetyl trimethylammonium bromide (C) 19 H 42 NBr) or dodecyltrimethylammonium bromide (C) 15 H 34 NBr)。
In the present invention, the molar ratio of the organic group to the inorganic group is preferably (6 to 3): 1, more preferably 4:1.
In the embodiment of the invention, the polymetallic oxygen cluster compound is H 4 SiW 12 O 40 The cationic surfactant is C 38 H 80 NBr is exemplified by the surfactant-embedded multi-metal oxygen cluster complex having the formula (C) 38 H 80 N) 4 SiW 12 O 40 Relative molecular mass m=5078.
The invention combines the multi-metal oxygen cluster compound with the cationic surfactant, combines the rigidity of inorganic materials and the flexibility of organic materials, and has good chemical stability; SEP film formed by embedding multi-metallic oxygen cluster compound based on the surfactant, wherein uniformly distributed multi-metallic oxygen cluster compound can be reduced in charging process, so that the whole multi-metallic oxygen cluster compound shows stronger electronegativity, thereby attracting more Zn 2+ Uniform deposition is beneficial to inhibiting dendrite generation and can significantly improve charge transfer kinetics. The hydrophobic alkyl chain of the surfactant can effectively isolate the metallic zinc electrode from water, thereby being beneficial to inhibiting corrosion and side reactions of the zinc electrode. The SEP film can adapt to volume change brought by a battery in the repeated zinc deposition and stripping processes, so that the zinc metal battery protected by the SEP film has longer cycle life.
The preparation method of the surfactant-embedded multi-metal oxygen cluster compound is not particularly limited, and the surfactant-embedded multi-metal oxygen cluster compound can be prepared by a method well known to a person skilled in the art. In the present invention, the preparation method of the surfactant-embedded multi-metal oxygen cluster complex preferably comprises the following steps:
mixing the multi-metal oxygen cluster compound, the cationic surfactant, chloroform and water, and carrying out embedding treatment to obtain the surfactant embedded multi-metal oxygen cluster compound.
In the present invention, the molar ratio of the cationic surfactant to the multi-metallic oxygen cluster compound is preferably (6 to 3): 1, more preferably 4:1. In the present invention, the mode of mixing the multi-metallic oxygen cluster compound, the cationic surfactant, chloroform and water preferably includes: mixing a multi-metallic oxygen cluster compound with water to obtain a multi-metallic oxygen cluster compound aqueous solution; mixing a cationic surfactant with chloroform to obtain a cationic surfactant chloroform solution; the cationic surfactant chloroform solution is added dropwise to the aqueous polyoxometalate compound solution under stirring. In the present invention, the concentration of the aqueous solution of the multi-metallic oxygen cluster compound is preferably 5 to 5.5mg/mL, more preferably 5.2mg/mL; the concentration of the chloroform solution of the cationic surfactant is preferably 22-25 mg/mL, more preferably 24mg/mL; the dosage of the chloroform solution of the cationic surfactant and the aqueous solution of the multi-metallic oxygen cluster compound is based on ensuring that the molar ratio of the cationic surfactant to the multi-metallic oxygen cluster compound meets the requirements; the dropping rate is preferably 8-12 mL/min, more preferably 10mL/min, and the effect of the dropping is preferably that the cationic surfactant fully replaces counter ions in the polyoxometalate so as to realize complete coating.
In the present invention, the temperature of the embedding treatment is preferably 20 to 30 ℃, and the embedding treatment may be specifically performed under the condition of room temperature (25 ℃); the time of the embedding treatment is preferably 0.5 to 1.5 hours, more preferably 1 hour; the embedding treatment time is counted from the completion of the dropwise addition of the chloroform solution of the cationic surfactant. In the present invention, the polymetallic oxygen cluster compound is H 4 SiW 12 O 40 The cationic surfactant is C 38 H 80 NBr (DODA) is exemplified, and anions formed by the multi-metallic oxygen cluster compound in the aqueous phase are transferred to the chloroform phase and DODA by electrostatic attraction during the embedding treatment + In combination, because chloroform and water are mutually insoluble, the generated surfactant is embedded with the polyoxometalate complex in chloroform phase, and HBr is dissolved in water phase.
After the embedding treatment is finished, the system obtained after the embedding treatment is preferably kept stand for layering, a chloroform phase is collected, washed and dried in sequence, and then chloroform is removed, so that the surfactant embedded multi-metal oxygen cluster compound is obtained. The system obtained after embedding treatment is preferably transferred into a separating funnel for standing delamination; the reagent used for washing is preferably secondary water, and the washing times are preferably 2-3 times; the drying agent adopted in the drying is preferably anhydrous sodium sulfate; the drying preferably further comprises filtration to remove the drying agent, and then chloroform is removed from the resulting filtrate by rotary evaporation, preferably at a temperature of 35 to 45 ℃, more preferably 40 ℃.
The invention provides an application of the surfactant-embedded multi-metal oxygen cluster compound prepared by the technical scheme or the surfactant-embedded multi-metal oxygen cluster compound prepared by the preparation method in a water system zinc ion battery.
The invention provides a zinc-based composite pole piece, which comprises a metal zinc sheet and an organic-inorganic hybridization modification layer modified on one side of the metal zinc sheet, wherein the organic-inorganic hybridization modification layer is made of the surfactant-embedded multi-metal oxygen cluster compound according to the technical scheme or the surfactant-embedded multi-metal oxygen cluster compound prepared by the preparation method according to the technical scheme. In the present invention, the thickness of the organic-inorganic hybrid modification layer is preferably 4 to 24nm, more preferably 12.5nm.
The invention provides a preparation method of the zinc-based composite pole piece, which comprises the following steps:
mixing the surfactant-embedded multi-metal oxygen cluster compound with an organic solvent to obtain a surfactant-embedded multi-metal oxygen cluster compound solution;
the surfactant-embedded multi-metal oxygen cluster compound solution is dripped on the water surface, and a film is formed on the water surface, so that the surfactant-embedded multi-metal oxygen cluster compound film is obtained;
and transferring the surfactant-embedded multi-metal oxygen cluster composite film to one side of a metal zinc sheet, and drying to form an organic-inorganic hybridization modification layer on one side of the metal zinc sheet to obtain the zinc-based composite pole piece.
The surfactant embedded multi-metal oxygen cluster compound (noted as SEP) in the invention can self-assemble at a water-air interface to form a uniform SEP film, and the SEP film is an amphiphilic film and has the following characteristics ofThe uniformity of the atomic size and the thickness are controllable, the nano-scale size requirement can be met, the nano-scale size requirement is convenient to transfer to the surface of a metal zinc sheet through an LB film technology to modify the metal zinc sheet, the obtained zinc-based composite pole piece is used as a negative electrode in a water-based zinc ion battery, and the ultrathin thickness of an SEP film and the uniform arrangement of SEP molecules are beneficial to accelerating zinc ion transmission kinetics; in addition, the SEP combines the rigidity of inorganic materials and the flexibility of organic materials, has good chemical stability, and can still exist stably in long-time electrochemical circulation. In the prior art, the SEI construction method comprises an in-situ method and a manual spin coating method; in-situ method generates SEI film through gas/solid reaction or liquid/solid reaction, SEI film thickness cannot be controlled, and thickness change in circulation process can influence Zn 2+ Transmission kinetics; SEI film surface non-uniformity prepared by manual spin coating method can influence Zn 2+ Uniform deposition and the addition of an adhesive increases the zinc ion transport resistance. The preparation method of the zinc-based composite pole piece in the invention is described in detail below.
The invention mixes the surfactant-embedded multi-metal oxygen cluster compound with an organic solvent to obtain a surfactant-embedded multi-metal oxygen cluster compound solution (marked as SEP solution). In the present invention, the concentration of the surfactant-embedded multi-metal oxide cluster complex in the SEP solution is preferably 1.5 to 2mM, more preferably 1.8mM. In the present invention, the organic solvent preferably includes chloroform or methylene chloride.
After the SEP solution is obtained, the SEP solution is dripped on the water surface, and a film is formed on the water surface, so that the SEP film is obtained. In the present invention, the rate of the dropping is preferably 1 to 4. Mu.L/s, more preferably 2. Mu.L/s. In the invention, the water surface is specifically an interface between water and air. In the embodiment of the invention, the secondary water is injected into the glass surface dish with the diameter of 8.5cm until the water level is slightly lower than the height of the glass surface dish, 20 mu L of SEP solution is dripped on the water surface at the rate of 2 mu L/s, chloroform is volatilized rapidly, and a uniform SEP film can be formed at the water-air interface by naked eyes. The invention preferably controls the thickness of the SEP film by controlling the dripping amount of the SEP solution.
After the SEP film is obtained, the SEP film is transferred to one side of a metal zinc sheet, and an organic-inorganic hybridization modification layer is formed on one side of the metal zinc sheet after drying, so that the zinc-based composite pole piece is obtained. In the present invention, the thickness of the metallic zinc sheet is preferably 0.2mm. According to the invention, a metal zinc sheet is preferably vertically stretched below a water interface at the edge of a glass surface dish, then an SEP film is transferred to the surface of the metal zinc sheet, and the metal zinc sheet is dried for 10min at 60 ℃ to completely evaporate water, so that the zinc-based composite pole piece is obtained.
The invention provides an application of the zinc-based composite pole piece prepared by the technical scheme or the preparation method of the technical scheme as a negative electrode of a water-based zinc ion battery. In the present invention, the aqueous zinc ion battery preferably includes a symmetrical battery or a half-cell, which will be described in detail below.
In the invention, the negative electrode and the positive electrode of the symmetrical battery are preferably zinc-based composite pole pieces (the symmetrical battery is named as SEP/Zn symmetrical battery), and the electrolyte of the symmetrical battery is preferably ZnSO 4 Aqueous solution of ZnSO 4 The concentration of the aqueous solution is preferably 2mol/L. In the present invention, the method for preparing the symmetrical battery preferably comprises the steps of: and sequentially assembling the cathode shell, the cathode, the spring piece, the gasket, the electrolyte, the diaphragm, the anode and the anode shell together, and then pressing to obtain the symmetrical battery. In the present invention, the separator is preferably glass fiber. The symmetrical cell is preferably prepared under room temperature conditions; the pressing pressure is preferably 800Pa.
In the invention, the negative electrode of the half cell is preferably bare Zn, the positive electrode is preferably a copper-based composite electrode (the half cell is named as Zn SEP/Cu half cell), and the electrolyte of the half cell is preferably ZnSO 4 Aqueous solution of ZnSO 4 The concentration of the aqueous solution is preferably 2mol/L. In the present invention, the preparation method of the half cell preferably includes the steps of: and assembling the cathode shell, the cathode, the spring piece, the gasket, the electrolyte, the diaphragm, the anode and the anode shell together in sequence, and then pressing to obtain the half-cell. In the present invention, the separator is preferably glass fiber. The invention is preferably carried out at room temperaturePreparing the half cell; the pressing pressure is preferably 800Pa.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1) Preparation of SEP: 1.2g of dioctadecyl dimethyl ammonium bromide (DODA, aba Ding Huaxue reagent Co.) was dissolved in 50mL of chloroform to obtain a DODA chloroform solution; will be 0.26g H 4 SiW 12 O 40 (Ala Ding Huaxue reagent Co.) in 50mL deionized water to give H 4 SiW 12 O 40 An aqueous solution; dropwise adding DODA chloroform solution to H at a rate of 10mL/min under stirring 4 SiW 12 O 40 In aqueous solution, to DODA and H 4 SiW 12 O 40 The molar ratio is 4:1, stopping dripping, wherein the system becomes turbid from clarification; stirring the obtained mixture at room temperature (25deg.C) for 1 hr, transferring to separating funnel, standing for delamination, collecting chloroform phase as lower layer and chloroform phase as upper layer, transferring to separating funnel, removing chloroform phase, washing with secondary water for 3 times, drying with anhydrous sodium sulfate, filtering, and rotary evaporating filtrate at 40deg.C to remove chloroform to obtain surfactant-embedded polyoxometalate complex, denoted SEP (molecular formula is (C) 38 H 80 N) 4 SiW 12 O 40 ，M＝5078)。
2) Preparation of SEP/Zn: dissolving SEP in chloroform to obtain SEP chloroform solution with concentration of 1.8 mM; injecting secondary water into a glass surface dish with the diameter of 8.5cm until the water level is slightly lower than the height of the glass surface dish, dripping 20 mu L of SEP chloroform solution onto the water surface at the rate of 2 mu L/s, quickly volatilizing chloroform, and observing that a uniform SEP film is formed at a water-air interface by naked eyes; zinc plates (area 4X 4 cm) 2 Thickness of 0.2 mm) is vertically extended below the water interface, and then S is addedThe EP film is transferred to the surface of a zinc sheet, and the zinc sheet containing the organic-inorganic hybridization modification layer is obtained after drying for 10min at 60 ℃ to enable water to be completely evaporated, and is marked as SEP/Zn.
The SEP film prepared in example 1 was characterized as well as SEP/Zn as follows:
fig. 1 is an SEM image of the SEP film on a zinc sheet and a corresponding EDS mapping image, and it is understood that the SEP film is uniformly and densely distributed over a large area, and Si, W, and C elements are uniformly distributed in the SEP film.
FIG. 2 is an AFM image of an SEP film, from which it can be seen that the SEP film thickness is very uniform, about 12.5nm.
Example 2
A zinc sheet containing an organic-inorganic hybrid modification layer was prepared in the same manner as in example 1 except that the amount of the SEP chloroform solution was changed to 40. Mu.L.
Comparative example 1
DODA was dissolved in chloroform to give a DODA chloroform solution at a concentration of 1.8 mM; injecting secondary water into a glass surface dish with the diameter of 8.5cm until the water level is slightly lower than the height of the glass surface dish, taking 20 mu L of DODA chloroform solution, dripping the DODA chloroform solution onto the water surface at the rate of 2 mu L/s, and enabling chloroform to volatilize rapidly so that a uniform DODA film can be observed to form at a water-air interface by naked eyes; zinc plate (4X 4 cm) 2 Thickness of 0.2 mm) is vertically stretched below the water interface, then the DODA film is transferred to the surface of the zinc sheet, and the zinc sheet containing the DODA film is obtained after drying for 10min at 60 ℃ to evaporate water completely, and is marked as DODA/Zn.
In the present invention, in order to demonstrate cationic surfactant (DODA) and polyoxometalate (H 4 SiW 12 O 40 ) The synergistic effect of hybridization was more effective in suppressing the generation of dendrites and byproducts, and button cells were prepared and tested for performance according to test example 1 and test example 2.
Test example 1
SEP/Zn prepared in examples 1-2, DODA/Zn prepared in comparative example 1 and zinc flakes were press-cut into pieces having an area of 0.785cm, respectively, using a tablet press 2 Obtaining an SEP/Zn pole piece, a DODA/Zn pole piece and bare Zn;
ZnSO at a concentration of 2mol/L 4 The aqueous solution is used as electrolyte, and based on the SEP/Zn pole piece, the DODA/Zn pole piece and the bare Zn, respectively assembling a water-based zinc ion button type symmetrical battery, specifically, under the room temperature condition, sequentially assembling a negative pole shell (CR 2032), a negative pole (the SEP/Zn pole piece, the DODA/Zn pole piece and the bare Zn respectively), a spring piece, a gasket, the electrolyte, a diaphragm (glass fiber), a positive pole (the SEP/Zn pole piece, the DODA/Zn pole piece and the bare Zn respectively) and the positive pole shell together, and then pressing under the 800Pa condition to obtain the water-based zinc ion button type symmetrical battery which is respectively marked as SEP/Zn I SEP/Zn, DODA/Zn I DODA/Zn and Zn I Zn;
by Zn 4 SiW 12 O 40 And ZnSO 4 The mixed aqueous solution of (2) is used as mixed electrolyte, and the water-based zinc ion button type symmetrical battery is assembled based on bare Zn, specifically, a negative electrode shell (CR 2032), a negative electrode (bare Zn), a spring piece, a gasket, mixed electrolyte, a diaphragm (glass fiber), a positive electrode (bare Zn) and a positive electrode shell are assembled together in sequence under the room temperature condition, and then pressed under the 800Pa condition to obtain the water-based zinc ion button type symmetrical battery, which is marked as Zn 4 SiW 12 O 40 /Zn||Zn 4 SiW 12 O 40 Zn; zn in the mixed electrolyte 4 SiW 12 O 40 Concentration of 1.8mM, znSO 4 The concentration was 2M.
Test example 2
Copper sheets containing organic-inorganic hybrid modified layers were prepared as in example 1, except that the zinc sheets were replaced with copper foil, designated SEP/Cu.
Pressing and cutting SEP/Cu, copper foil and zinc sheet into 0.785cm 2 Obtaining SEP/Cu pole pieces, bare Cu and bare Zn;
ZnSO at a concentration of 2mol/L 4 The aqueous solution is used as electrolyte, based on the SEP/Cu pole piece, the bare Cu and the bare Zn, the water-based zinc ion button half cell is assembled respectively, specifically, a negative electrode shell (CR 2032), a negative electrode (bare Zn), a spring piece, a gasket, electrolyte, a diaphragm (glass fiber), a positive electrode (SEP/Cu pole piece and bare Cu respectively) and a positive electrode shell are assembled in sequence under the condition of room temperatureAnd then pressing under 800Pa to obtain a water-based zinc ion button half cell, which is respectively marked as Zn SEP/Cu and Zn Cu.
The button cells prepared in test example 1 and test example 2 were respectively clamped in a blue electrochemical tester, and electrochemical stability cycle test was performed.
FIG. 3 is a symmetrical battery SEP/Zn and Zn DODA/Zn and Zn DODA/Zn based on SEP/Zn assembly in example 1 4 SiW 12 O 40 /Zn||Zn 4 SiW 12 O 40 Zn under high current density (current density of 10 mA/cm) 2 The capacity is 1mAh/cm 2 ) From the graph, it can be seen that the SEP/Zn prepared in example 1 has longer cycle life and smaller polarization voltage than bare Zn, while DODA/Zn and multi-metal oxide cluster Zn 4 SiW 12 O 40 Electrolyte additives are longer life than bare Zn, but worse than SEP/Zn.
FIG. 4 is a graph of the current density of a symmetric battery SEP/Zn under high current density conditions (current density of 10 mA/cm) based on SEP/Zn assembly in example 2 2 The capacity is 1mAh/cm 2 ) Cycle life graph it can be seen that increasing the thickness of the SEP film reduces the cycling stability of the zinc electrode.
FIG. 5 shows the half cell Zn SEP/Cu and Zn Cu under a small current density (current density of 2 mA/cm) 2 The capacity is 1mAh/cm 2 ) From the graph, the half cell based on SEP/Cu assembly can stably cycle 3700 circles and maintain 99.97% coulombic efficiency compared to bare Cu.
FIG. 6 shows that the Zn concentration of the symmetric battery is 10mA/cm under the condition of high current density (current density is 10 mA/cm) 2 The capacity is 1mAh/cm 2 ) The scanning electron microscope image (two-electrode system) of the bare Zn cathode after 600 circles is circulated, and the surface of the bare Zn cathode becomes uneven due to uneven deposition of zinc ions.
FIG. 7 is a diagram of a symmetric battery SEP/Zn under high current density conditions (current density of 10 mA/cm) based on SEP/Zn assembly in example 1 2 The capacity is 1mAh/cm 2 ) Scanning of SEP/Zn negative electrode after 600 circlesIn the electron microscope image (two-electrode system), it can be seen that the surface of the SEP/Zn negative electrode is flat because zinc ions are uniformly deposited on the surface of the SEP/Zn negative electrode.
Fig. 8 is a graph (three electrode system) comparing corrosion curves of bare Zn negative electrode in symmetric battery Zn and SEP/Zn negative electrode in SEP/Zn based on SEP/Zn assembled symmetric battery in example 1, from which it can be seen that SEP/Zn negative electrode has smaller corrosion current density and more corrected corrosion voltage, indicating less corrosion trend and slower corrosion rate than bare Zn negative electrode.
FIG. 9 is a SEP/Zn symmetric battery at 10mA/cm based on SEP/Zn assembly in example 1 2 X-ray photoelectron spectroscopy (XPS) at the end of the cycle. From the figure it can be seen that W in the poly-metal-oxygen cluster 6+ Is reduced to W 5+ Resulting in an increase in electronegativity of the uniformly arranged multi-metallic oxygen cluster compound, which can induce uniform and rapid deposition of zinc ions onto the surface of the zinc electrode, thereby inhibiting dendrite growth.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The application of a surfactant-embedded multi-metal oxygen cluster compound in zinc electrode protection comprises inorganic groups and organic groups which are combined through electrostatic action, wherein the raw material for providing the inorganic groups is a multi-metal oxygen cluster compound, and the raw material for providing the organic groups is a cationic surfactant; the zinc electrode is a negative electrode of the water-based zinc ion battery.
2. The use according to claim 1, wherein the anions of the multi-metallic oxygen cluster compound comprise [ PW 12 O 40 ] 3- 、[SiW 12 O 40 ] 4- Or [ P ] 2 W 18 O 62 ] 6- Counter ions include H + 、Na + Or K + 。
3. Use according to claim 1, wherein the cationic surfactant comprises dioctadecyl dimethyl ammonium bromide, tetraheptyl ammonium bromide, cetyl trimethyl ammonium bromide or dodecyl trimethyl ammonium bromide.
4. Use according to any one of claims 1 to 3, characterized in that the molar ratio of organic groups to inorganic groups is (3 to 6): 1.
5. the zinc-based composite pole piece comprises a metal zinc sheet and an organic-inorganic hybridization modification layer modified on one side of the metal zinc sheet, wherein the organic-inorganic hybridization modification layer is made of a surfactant embedded multi-metal oxygen cluster compound; the surfactant embedded multi-metal oxygen cluster compound comprises an inorganic group and an organic group which are combined through electrostatic action, wherein the raw material for providing the inorganic group is a multi-metal oxygen cluster compound, and the raw material for providing the organic group is a cationic surfactant.
6. The zinc-based composite pole piece of claim 5, wherein the thickness of the organic-inorganic hybrid modification layer is 4-24 nm.
7. The method for preparing the zinc-based composite pole piece according to claim 5 or 6, comprising the following steps:
mixing the surfactant-embedded multi-metal oxygen cluster compound with an organic solvent to obtain a surfactant-embedded multi-metal oxygen cluster compound solution;
the surfactant-embedded multi-metal oxygen cluster compound solution is dripped on the water surface, and a film is formed on the water surface, so that the surfactant-embedded multi-metal oxygen cluster compound film is obtained;
and transferring the surfactant-embedded multi-metal oxygen cluster composite film to one side of a metal zinc sheet, and drying to form an organic-inorganic hybridization modification layer on one side of the metal zinc sheet to obtain the zinc-based composite pole piece.
8. The method according to claim 7, wherein the concentration of the surfactant-embedded multi-metal oxygen cluster composite solution is 1.5 to 2mmol/L, and the dropping rate of the surfactant-embedded multi-metal oxygen cluster composite solution is 1 to 4 μl/s.
9. Application of the zinc-based composite pole piece prepared by the preparation method of claim 5 or 6 or claim 7 or 8 as a negative electrode of a water-based zinc ion battery.
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