CN114899347A - 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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- 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
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 62
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- 101150034825 DODA gene Proteins 0.000 description 26
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 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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- 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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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, and belongs to the technical field of functional materials. The polymetallic oxygen cluster compound and the cationic surfactant are compounded through electrostatic action, the obtained surfactant-embedded polymetallic oxygen cluster compound (marked as SEP) can be self-assembled at a water-air interface to form a uniform SEP film, the SEP film is an amphiphilic film, has the uniformity of atomic size, has controllable thickness, can meet the requirement of nanoscale size, is convenient to transfer to the surface of a metal zinc sheet through an LB (Langmuir-Blodgett) film technology to realize the modification of the metal zinc sheet, and the obtained zinc-based composite pole piece is used as a negative electrode in a water-based zinc ion battery to be beneficial to accelerating the transmission kinetics of zinc ions; and the SEP combines the rigidity of inorganic materials and the flexibility of organic materials, has good chemical stability, and the SEP film structure can still exist stably in long-term 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 have received much attention 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 due to non-uniform zinc ion deposition is one of the causes of the problem, and further development of the aqueous zinc ion battery is limited.
By constructing a Solid Electrolyte Interface (SEI) between the zinc metal cathode and the electrolyte, zinc ions are induced to be uniformly deposited, dendritic crystal growth can be avoided, and meanwhile corrosion of the electrolyte to the zinc metal cathode can be effectively isolated. At present, SEI (solid electrolyte interphase) construction materials comprise organic materials, inorganic materials or organic-inorganic hybrid materials, the organic materials have the flexibility but the mechanical strength is poor, 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 the conditions of large current density and rapid charge and discharge. Therefore, the combination of organic materials and inorganic materials 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 has uneven thickness and is usually thick, and is easy to cause uneven deposition of zinc ions on the surface of an electrode and slow migration kinetics of the zinc ions (Angew. chem. 2020,132, 16737-.
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.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an application of a surfactant embedded multi-metal oxygen cluster compound in zinc electrode protection, wherein the surfactant embedded multi-metal oxygen cluster compound comprises an inorganic group and an organic group which are combined through electrostatic action, 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.
Preferably, the anion of the multimetal oxygen cluster compound comprises [ PW 12 O 40 ] 3- 、[SiW 12 O 40 ] 4- Or [ P 2 W 18 O 62 ] 6- The counter ion comprises H + 、Na + Or K + 。
Preferably, the cationic surfactant comprises dioctadecyldimethylammonium bromide, tetraheptylammonium bromide, hexadecyltrimethylammonium bromide or dodecyltrimethylammonium bromide.
Preferably, the molar ratio of the organic group to the inorganic group 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 piece and an organic-inorganic hybrid modification layer modified on one side of the metal zinc piece, wherein the organic-inorganic hybrid modification layer is made of a surfactant-embedded multi-metal oxygen cluster compound.
Preferably, the thickness of the organic-inorganic hybrid modification layer is 4-24 nm.
The invention provides a preparation method of the zinc-based composite pole piece in the technical scheme, which comprises the following steps:
mixing the surfactant-embedded polyoxometalate compound with an organic solvent to obtain a surfactant-embedded polyoxometalate compound solution;
dropwise adding the surfactant-embedded polyoxometalate compound solution to the water surface, and forming a film on the water surface to obtain a surfactant-embedded polyoxometalate compound film;
and transferring the surfactant embedded multi-metal oxygen cluster compound film to the single surface of a metal zinc sheet, and forming an organic-inorganic hybrid modification layer on the single surface of the metal zinc sheet after drying to obtain the zinc-based composite pole piece.
Preferably, the concentration of the surfactant embedded polyoxometalate compound solution is 1.5-2 mmol/L, and the dropping rate of the surfactant embedded polyoxometalate compound solution is 1-4 mu L/s.
The invention provides an application of the zinc-based composite pole piece in the technical scheme or the zinc-based composite pole piece prepared by the preparation method in the technical scheme as a cathode of a water system zinc ion battery.
The invention provides an application of a surfactant embedded multi-metal oxygen cluster compound in zinc electrode protection, wherein the surfactant embedded multi-metal oxygen cluster compound comprises an inorganic group and an organic group which are combined through electrostatic action, 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. The invention compounds the polyoxometalate compound and the cationic surfactant through electrostatic interaction, the obtained surfactant-embedded polyoxometalate compound (marked as SEP) can be self-assembled at a water-air interface to form a uniform SEP film, the SEP film is an amphiphilic film and has the advantages of atom size uniformity and controllable thickness, can meet the requirement of nano-scale size, is convenient to transfer to the surface of a metal zinc sheet through LB film technology to realize the modification of the metal zinc sheet, and the obtained zinc-based composite pole piece (marked as SEP/Zn) is used as a negative pole in a water-system zinc ion battery, the ultrathin thickness of the SEP film and the uniform arrangement of SEP molecules are favorable for accelerating the zinc ion transmission kinetics, the function coordination of the multi-metal oxygen cluster compound and the cationic surfactant in the SEP film can realize the uniform deposition of zinc ions and effectively inhibit dendritic crystals, thereby realizing the cycle reversibility; in addition, the SEP film structure has good chemical stability by combining the rigidity of inorganic materials and the flexibility of organic materials, and the SEP film structure can still exist stably in long-term electrochemical circulation.
Drawings
FIG. 1 is an SEM image of an SEP film prepared in example 1 on a zinc sheet and the corresponding EDS mapping image;
FIG. 2 is an AFM image of the SEP film prepared in example 1;
FIG. 3 is a diagram of symmetric batteries SEP/Zn | | | SEP/Zn and Zn | | | Zn, DODA/Zn | | | DODA/Zn and Zn based on the SEP/Zn assembly in example 1 4 SiW 12 O 40 /Zn||Zn 4 SiW 12 O 40 a/Zn cycle life comparison graph under a high current density condition;
FIG. 4 is a graph of the cycle life of a symmetric battery SEP/Zn | | | SEP/Zn based on the SEP/Zn assembly in example 2 under high current density conditions;
FIG. 5 is a coulombic efficiency comparison graph 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 symmetric Zn under a high current density condition;
FIG. 7 is a Scanning Electron Microscope (SEM) image of the SEP/Zn negative electrode after 600 cycles of the SEP/Zn based on the SEP/Zn assembly in example 1 under the condition of high current density;
fig. 8 is a comparison graph of corrosion curves for bare Zn negative electrodes in symmetric Zn and SEP/Zn negative electrodes in symmetric cells SEP/Zn assembled based on SEP/Zn in example 1;
FIG. 9 shows an SEP/Zn | SEP/Zn symmetrical battery at 10mA/cm based on the SEP/Zn assembly in example 1 2 XPS plots at the end of charging after cycling.
Detailed Description
The invention provides an application of a surfactant embedded multi-metal oxygen cluster compound in zinc electrode protection, wherein the surfactant embedded multi-metal oxygen cluster compound comprises an inorganic group and an organic group which are combined through electrostatic action, 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.
In the present invention, the zinc electrode is preferably a negative electrode of an aqueous zinc ion battery.
In the present invention, the anion of the multimetal oxygen cluster compound preferably comprises [ 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 comprises dioctadecyldimethylammonium bromide (C) 38 H 80 NBr), Tetraheptyl ammonium bromide (C) 28 H 60 NBr), cetyl trimethylammonium bromide (C) 19 H 42 NBr) or dodecyl trimethyl ammonium 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 multi-metal oxygen cluster compound is H 4 SiW 12 O 40 The cationic surfactant is C 38 H 80 NBr is an example, the molecular formula of the surfactant embedded polyoxometalate complex is (C) 38 H 80 N) 4 SiW 12 O 40 Relative molecular mass M5078.
The invention compounds the multi-metal oxygen cluster compound and the cationic surfactant, combines the rigidity of inorganic materials and the flexibility of organic materials, and has good chemical stability; the SEP film formed by embedding the polyoxometalate compound based on the surfactant can reduce the uniformly distributed polyoxometalate compound in the charging process, so that the whole polyoxometalate compound has stronger electronegativity and can attract more Zn 2+ Uniform deposition is beneficial to inhibiting the generation of dendrite and obviously improving charge transfer kinetics. The hydrophobic alkyl chain of the surfactant can effectively isolate the metal zinc electrode from water, thereby being beneficial to inhibiting the corrosion of the zinc electrode and the occurrence of side reactions. The SEP film can accommodate the volume change of the cell during repeated zinc deposition and stripping,the SEP film protected zinc metal battery has longer cycle life.
The preparation method of the surfactant embedded polyoxometalate compound is not particularly limited, and the surfactant embedded polyoxometalate compound can be prepared by a method well known to those skilled in the art. In the present invention, the preparation method of the surfactant-embedded polyoxometalate complex preferably comprises the following steps:
mixing the polyoxometalate compound, the cationic surfactant, chloroform and water, and carrying out embedding treatment to obtain the surfactant-embedded polyoxometalate compound.
In the present invention, the molar ratio of the cationic surfactant to the multimetal oxygen cluster compound is preferably (6 to 3): 1, more preferably 4: 1. In the present invention, the manner of mixing the multimetal oxide cluster compound, the cationic surfactant, and chloroform with water preferably includes: mixing a polymetallic oxygen cluster compound with water to obtain a polymetallic oxygen cluster compound aqueous solution; mixing a cationic surfactant with chloroform to obtain a cationic surfactant chloroform solution; and dropwise adding the cationic surfactant chloroform solution into the aqueous solution of the multi-metal oxygen cluster compound under stirring. In the invention, the concentration of the aqueous solution of the polyoxometalate compound is preferably 5-5.5 mg/mL, and more preferably 5.2 mg/mL; the concentration of the cationic surfactant chloroform solution is preferably 22-25 mg/mL, and more preferably 24 mg/mL; the dosage of the cationic surfactant chloroform solution and the multi-metal oxygen cluster compound aqueous solution is based on the condition that the molar ratio of the cationic surfactant to the multi-metal oxygen cluster compound meets the requirement; the dripping rate is preferably 8-12 mL/min, more preferably 10mL/min, and the invention preferably adopts the dripping effect to enable the cationic surfactant to fully replace counter ions in the polyoxometalate cluster so as to realize complete coating.
In the invention, the embedding temperature is preferably 20-30 ℃, and the embedding treatment can be carried out at room temperature (25 ℃); the embedding time is preferably 0.5-1.5 h, and more preferably 1 h; the embedding treatment is carried out for a long time in a cationic mannerAnd counting after the chloroform solution of the sub-type surfactant is added. In the present invention, the multi-metal oxygen cluster compound is H 4 SiW 12 O 40 The cationic surfactant is C 38 H 80 NBr (DODA) for example, in the process of the embedding treatment, anions formed by the polyoxometalate compound in the aqueous phase are transferred to the chloroform phase by electrostatic attraction to react with DODA + In combination, as chloroform and water are not mutually soluble, the generated surfactant embeds the polyoxometalate complex in a chloroform phase, and HBr is dissolved in a 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 and is washed and dried in sequence, and then the chloroform is removed, so that the surfactant embedded polyoxometalate compound is obtained. Preferably, the system obtained after embedding treatment is transferred to a separating funnel for standing and layering; the reagent used for washing is preferably secondary water, and the washing frequency is preferably 2-3 times; the drying agent used for drying is preferably anhydrous sodium sulfate; preferably, the drying process further comprises filtering to remove a drying agent, and then removing chloroform in the obtained filtrate through rotary evaporation, wherein the temperature of the rotary evaporation is preferably 35-45 ℃, and more preferably 40 ℃.
The invention provides an application of the surfactant embedded multi-metal oxygen cluster compound in the technical scheme or the surfactant embedded multi-metal oxygen cluster compound prepared by the preparation method in the technical scheme in a water-based zinc ion battery.
The invention provides a zinc-based composite pole piece, which comprises a metal zinc sheet and an organic-inorganic hybrid modification layer modified on one side of the metal zinc sheet, wherein the organic-inorganic hybrid modification layer is made of the surfactant embedded multi-metal oxygen cluster compound in the technical scheme or the surfactant embedded multi-metal oxygen cluster compound prepared by the preparation method in the technical scheme. In the invention, the thickness of the organic-inorganic hybrid modification layer is preferably 4-24 nm, and more preferably 12.5 nm.
The invention provides a preparation method of the zinc-based composite pole piece in the technical scheme, which comprises the following steps:
mixing the surfactant-embedded polyoxometalate compound with an organic solvent to obtain a surfactant-embedded polyoxometalate compound solution;
dropwise adding the surfactant-embedded polyoxometalate compound solution to the water surface, and forming a film on the water surface to obtain a surfactant-embedded polyoxometalate compound film;
and transferring the surfactant embedded multi-metal oxygen cluster compound film to the single surface of a metal zinc sheet, and forming an organic-inorganic hybrid modification layer on the single surface of the metal zinc sheet after drying to obtain the zinc-based composite pole piece.
The surfactant-embedded multi-metal oxygen cluster compound (marked as 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 the requirement of nanoscale size, is convenient to transfer to the surface of a metal zinc sheet by an LB (cubic boron-based) film technology to realize the modification of the metal zinc sheet, the obtained zinc-based composite pole piece is used as a negative electrode in a water system zinc ion battery, and the ultrathin thickness of the SEP film and the uniform arrangement of SEP molecules are favorable for accelerating the zinc ion transmission dynamics; in addition, the SEP film structure has good chemical stability by combining the rigidity of inorganic materials and the flexibility of organic materials, and the SEP film structure can still exist stably in long-term electrochemical circulation. In the prior art, methods for constructing SEI include an in-situ method and a manual spin coating method; the in-situ method generates an SEI film through gas/solid reaction or liquid/solid reaction, the thickness of the SEI film cannot be controlled, and the thickness of the SEI film changes in the circulating process, which affects Zn 2+ Transport kinetics; the surface of SEI film prepared by the artificial spin-coating method is not uniform, and Zn can be influenced 2+ Uniform deposition and the need for an adhesive increase the zinc ion transport resistance. The preparation method of the zinc-based composite pole piece is explained in detail below.
The method comprises the step of mixing a surfactant embedded polyoxometalate compound with an organic solvent to obtain a surfactant embedded polyoxometalate compound solution (marked as SEP solution). In the invention, the concentration of the surfactant embedded polyoxometalate complex in the SEP solution is preferably 1.5-2 mM, and more preferably 1.8 mM. In the present invention, the organic solvent preferably includes chloroform or dichloromethane.
After the SEP solution is obtained, the SEP solution is dripped to the water surface to form a film on the water surface, so that the SEP film is obtained. In the invention, the dripping speed is preferably 1-4 mu L/s, and more preferably 2 mu L/s. In the present invention, the water surface is specifically an interface of water and air. In the embodiment of the invention, the secondary water is injected into a glass surface dish with the diameter of 8.5cm until the horizontal plane is slightly lower than the height of the glass surface dish, 20 mu L of SEP solution is dripped into the water surface at the speed of 2 mu L/s, chloroform is volatilized rapidly, and a uniform SEP film can be observed to be formed on the water-air interface by naked eyes. The invention preferably controls the thickness of the SEP film by controlling the dropping amount of the SEP solution.
After the SEP film is obtained, the SEP film is transferred to the single surface of a metal zinc sheet, and an organic-inorganic hybrid modification layer is formed on the single surface 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 0.2 mm. According to the invention, the metal zinc sheet is preferably vertically stretched below a water interface at the edge of a glass surface dish, then the SEP film is transferred to the surface of the metal zinc sheet, and the metal zinc sheet is dried at 60 ℃ for 10min 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 in the technical scheme or the zinc-based composite pole piece prepared by the preparation method in the technical scheme as a cathode of a water system zinc ion battery. In the present invention, the aqueous zinc ion battery preferably includes a symmetrical battery or a half battery, 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 marked as an SEP/Zn symmetrical battery), and the electrolyte of the symmetrical battery is preferably ZnSO 4 An aqueous solution of the ZnSO 4 The concentration of the aqueous solution is preferably 2 mol/L. In the present invention, the method for preparing the symmetrical battery preferably comprises the following steps: assembling the negative electrode shell, the negative electrode, the spring piece, the gasket, the electrolyte, the diaphragm, the positive electrode and the positive electrode shell together in sequence, and then pressing to obtain the anode materialTo a symmetrical cell. In the present invention, the separator is preferably glass fiber. The invention preferably prepares the symmetrical battery under the condition of room temperature; the pressure of the pressing is preferably 800 Pa.
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 marked as Zn SEP/Cu half-cell), and the electrolyte of the half-cell is preferably ZnSO 4 An aqueous solution of the ZnSO 4 The concentration of the aqueous solution is preferably 2 mol/L. In the present invention, the method for manufacturing the half cell preferably includes the steps of: and assembling the negative electrode shell, the negative electrode, the spring piece, the gasket, the electrolyte, the diaphragm, the positive electrode and the positive electrode shell together in sequence, and then pressing to obtain the half-cell. In the present invention, the separator is preferably glass fiber. The present invention preferably prepares the half-cell at room temperature; the pressure of the pressing is preferably 800 Pa.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1) Preparation of SEP: dissolving 1.2g dioctadecyldimethylammonium bromide (DODA, Allantin Chemicals Co.) in 50mL chloroform to obtain a DODA chloroform solution; 0.26g H 4 SiW 12 O 40 (Aladdin Chemicals Co.) in 50mL of deionized water to give H 4 SiW 12 O 40 An aqueous solution; the DODA chloroform solution was added dropwise to H at a rate of 10mL/min with 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 turns from clear to turbid; stirring the obtained mixed solution at room temperature (25 deg.C) for 1 hr, transferring into separating funnel, standing for layering, collecting the lower layer of chloroform phase and the upper layer of water phase, and separating from the separating funnelTransferring chloroform phase, washing with secondary water for 3 times, drying with anhydrous sodium sulfate, filtering, and rotary evaporating the filtrate at 40 deg.C to remove chloroform to obtain surfactant-embedded polyoxometalate complex (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 horizontal plane is slightly lower than the height of the glass surface dish, dripping 20 mu L of SEP chloroform solution on the water surface at the speed of 2 mu L/s, and rapidly volatilizing the chloroform to observe that a layer of uniform SEP film is formed on a water-air interface by naked eyes; zinc flakes (area 4X 4 cm) were applied to the edge of the glass cuvette 2 0.2mm in thickness) vertically extending below the water interface, then transferring the SEP film to the surface of a zinc sheet, drying at 60 ℃ for 10min to completely evaporate water, and obtaining the zinc sheet containing the inorganic-inorganic hybrid modification layer, which is marked as SEP/Zn.
The SEP films prepared in example 1 and SEP/Zn were characterized as follows:
fig. 1 is an SEM image and the corresponding EDS mapping image of the SEP film on a zinc plate, and it can be seen that the SEP film is uniformly and densely distributed over a large area and the Si, W, and C elements are uniformly distributed in the SEP film.
Fig. 2 is an AFM image of the SEP film, from which it can be seen that the SEP film has a very uniform thickness of about 12.5 nm.
Example 2
A zinc sheet containing an organic-inorganic hybrid modified layer was prepared as in example 1, except that the amount of the SEP chloroform solution was changed to 40. mu.L.
Comparative example 1
Dissolving DODA in chloroform to obtain a DODA chloroform solution with the concentration of 1.8 mM; injecting secondary water into a glass surface dish with the diameter of 8.5cm until the horizontal plane is slightly lower than the height of the glass surface dish, dropwise adding 20 mu L of DODA chloroform solution onto the water surface at the speed of 2 mu L/s, and rapidly volatilizing chloroform to form a uniform DODA film on a water-air interface by naked eyes; zinc plate (4X 4 cm) on the edge of glass surface dish 2 Thickness of0.2mm) vertically below the water interface, then transferring the DODA film to the surface of a zinc sheet, drying at 60 ℃ for 10min to completely evaporate water, and obtaining the zinc sheet containing the DODA film, which is recorded as DODA/Zn.
In the present invention, to demonstrate cationic surfactant (DODA) and polyoxometalate (H) 4 SiW 12 O 40 ) The synergistic effect caused by hybridization can more effectively inhibit the generation of dendrites and byproducts, and the button cell is prepared and subjected to performance test according to test examples 1 and 2.
Test example 1
SEP/Zn prepared in examples 1-2, DODA/Zn prepared in comparative example 1 and zinc sheets were each press-cut using a tablet press to an area of 0.785cm 2 Obtaining an SEP/Zn pole piece, a DODA/Zn pole piece and naked Zn by the wafer;
ZnSO with a concentration of 2mol/L 4 The water-based zinc ion button-type symmetric battery is prepared by using an aqueous solution as an electrolyte, respectively assembling a water-based zinc ion button-type symmetric battery based on the SEP/Zn pole piece, the DODA/Zn pole piece and the bare Zn, and specifically assembling a negative electrode shell (CR2032), a negative electrode (respectively the SEP/Zn pole piece, the DODA/Zn pole piece and the bare Zn), a spring piece, a gasket, an electrolyte, a diaphragm (glass fiber), a positive electrode (respectively the SEP/Zn pole piece, the DODA/Zn pole piece and the bare Zn) and a positive electrode shell together in sequence at room temperature, and then pressing under the condition of 800Pa to obtain the water-based zinc ion button-type symmetric battery, which is respectively marked as SEP/Zn | | SEP/Zn, DODA/Zn | DODA/Zn and Zn | Zn;
with Zn 4 SiW 12 O 40 And ZnSO 4 The mixed aqueous solution is used as mixed electrolyte, a water system zinc ion button type symmetrical battery is assembled based on bare Zn, specifically, a negative electrode shell (CR2032), a negative electrode (bare Zn), a spring piece, a gasket, the mixed electrolyte, a diaphragm (glass fiber), a positive electrode (bare Zn) and a positive electrode shell are assembled together in sequence at room temperature, and then the mixture is pressed under the condition of 800Pa to obtain the water system zinc ion button type symmetrical battery, which is marked as Zn button type symmetrical battery 4 SiW 12 O 40 /Zn||Zn 4 SiW 12 O 40 Zn; zn in the mixed electrolyte 4 SiW 12 O 40 At a concentration of 1.8mM, ZnSO 4 The concentration was 2M.
Test example 2
Copper sheets containing organic-inorganic hybrid finish layers were prepared as in example 1, except that the zinc sheets were replaced with copper foil, noted SEP/Cu.
Pressing and cutting SEP/Cu and copper foil and zinc sheet into pieces with area of 0.785cm by using a tablet press 2 Obtaining an SEP/Cu pole piece, bare Cu and bare Zn;
ZnSO with a concentration of 2mol/L 4 And (2) respectively assembling a water-based zinc ion button half cell by taking the aqueous solution as an electrolyte based on the SEP/Cu pole piece, the bare Cu and the bare Zn, specifically assembling a negative electrode shell (CR2032), a negative electrode (bare Zn), a spring piece, a gasket, the electrolyte, a diaphragm (glass fiber), a positive electrode (the SEP/Cu pole piece and the bare Cu respectively) and a positive electrode shell together in sequence at room temperature, and then pressing under the condition of 800Pa to obtain the water-based zinc ion button half cell which is respectively marked as Zn | | | SEP/Cu and Zn | | Cu.
The button cells prepared in test examples 1 and 2 were respectively inserted into a blue electrochemical tester to perform an electrochemical stability cycle test.
FIG. 3 is a diagram of symmetric batteries SEP/Zn | | | SEP/Zn and Zn | | | Zn, DODA/Zn | | | DODA/Zn and Zn based on the SEP/Zn assembly in example 1 4 SiW 12 O 40 /Zn||Zn 4 SiW 12 O 40 Zn under the condition of high current density (the current density is 10 mA/cm) 2 Capacity of 1mAh/cm 2 ) The graph shows that the SEP/Zn prepared in example 1 has longer cycle life and smaller polarization voltage compared with the bare Zn, and simultaneously DODA/Zn and multi-metal oxygen cluster Zn 4 SiW 12 O 40 The electrolyte additives all have longer life than bare Zn, but are inferior to SEP/Zn.
FIG. 4 is a diagram of a symmetric SEP/Zn cell based on the SEP/Zn assembly in example 2 under high current density conditions (current density of 10 mA/cm) 2 Capacity of 1mAh/cm 2 ) Cycle life figure, it can be seen that increasing the thickness of the SEP film reduces the cycling stability of the zinc electrode.
FIG. 5 shows half-cells Zn | | | SEP/Cu and Zn | | | | Cu under the condition of low current density (The current density is 2mA/cm 2 Capacity of 1mAh/cm 2 ) From the graph, it can be seen that the half cell based on SEP/Cu assembly can stabilize 3700 cycles of cycling and maintain 99.97% coulombic efficiency compared to bare Cu.
FIG. 6 shows symmetric Zn under high current density (current density 10 mA/cm) 2 Capacity of 1mAh/cm 2 ) And (3) a scanning electron microscope image (two-electrode system) of the bare Zn negative electrode after 600 cycles of circulation shows that the surface of the bare Zn negative electrode becomes uneven due to uneven zinc ion deposition.
FIG. 7 is a diagram of a symmetric SEP/Zn based on the SEP/Zn assembly in example 1 under high current density conditions (current density of 10 mA/cm) 2 Capacity of 1mAh/cm 2 ) After 600 cycles, the SEP/Zn cathode is subjected to a scanning electron microscope (two-electrode system), and as can be seen from the figure, zinc ions are uniformly deposited on the surface of the SEP/Zn cathode, the surface of the SEP/Zn cathode is smooth.
Fig. 8 is a comparison graph of corrosion curves for bare Zn negative electrodes in symmetric Zn | | | Zn and for SEP/Zn negative electrodes in symmetric cells SEP/Zn based on the SEP/Zn assembly in example 1 (three-electrode system), from which it can be seen that SEP/Zn negative electrodes possess smaller corrosion current densities and more positive corrosion voltages, indicating less corrosion tendency and slower corrosion rates, compared to bare Zn negative electrodes.
FIG. 9 shows an SEP/Zn | SEP/Zn symmetrical battery at 10mA/cm based on the SEP/Zn assembly in example 1 2 X-ray photoelectron spectroscopy (XPS) at the end of charging after cycling. From the figure, W in the polyoxometalate cluster can be seen 6+ Is reduced to W 5+ Leading to the increase of electronegativity of the uniformly arranged multi-metal oxygen cluster compound, which can induce the uniform and rapid deposition of zinc ions on the surface of the zinc electrode, thereby inhibiting the growth of dendrites.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The application of a surfactant embedded multi-metal oxygen cluster compound in zinc electrode protection is characterized in that the surfactant embedded multi-metal oxygen cluster compound comprises an inorganic group and an organic group which are combined through electrostatic action, 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.
2. The use of claim 1, wherein the anion of the multimetal oxygen cluster compound comprises [ PW 12 O 40 ] 3- 、[SiW 12 O 40 ] 4- Or [ P 2 W 18 O 62 ] 6- The counter ion comprises H + 、Na + Or K + 。
3. Use according to claim 1, characterized in that the cationic surfactant comprises dioctadecyldimethylammonium bromide, tetraheptylammonium bromide, cetyltrimethylammonium bromide or dodecyltrimethylammonium bromide.
4. Use according to any one of claims 1 to 3, wherein the molar ratio of organic groups to inorganic groups is (3 to 6): 1.
5. use according to claim 1, wherein the zinc electrode is the negative electrode of an aqueous zinc-ion battery.
6. A zinc-based composite pole piece comprises a metal zinc sheet and an organic-inorganic hybrid modification layer modified on one side of the metal zinc sheet, wherein the organic-inorganic hybrid modification layer is made of a surfactant-embedded multi-metal oxygen cluster compound.
7. The zinc-based composite pole piece according to claim 6, wherein the organic-inorganic hybrid modification layer has a thickness of 4-24 nm.
8. A method of making a zinc-based composite pole piece according to claim 6 or 7, comprising the steps of:
mixing the surfactant-embedded polyoxometalate compound with an organic solvent to obtain a surfactant-embedded polyoxometalate compound solution;
dropwise adding the surfactant-embedded polyoxometalate compound solution to the water surface, and forming a film on the water surface to obtain a surfactant-embedded polyoxometalate compound film;
and transferring the surfactant embedded multi-metal oxygen cluster compound film to the single surface of a metal zinc sheet, and forming an organic-inorganic hybrid modification layer on the single surface of the metal zinc sheet after drying to obtain the zinc-based composite pole piece.
9. The preparation method according to claim 8, wherein the concentration of the surfactant-embedded polyoxometalate complex solution is 1.5 to 2mmol/L, and the dropping rate of the surfactant-embedded polyoxometalate complex solution is 1 to 4 μ L/s.
10. The application of the zinc-based composite pole piece in claim 6 or 7 or the zinc-based composite pole piece prepared by the preparation method in claim 8 or 9 as a negative electrode of an aqueous zinc ion battery.
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