CN115838557B - Preparation method of high-molecular functional coating for metal negative electrode - Google Patents
Preparation method of high-molecular functional coating for metal negative electrode Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
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- 238000012986 modification Methods 0.000 claims abstract description 31
- 230000004048 modification Effects 0.000 claims abstract description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 18
- 239000011701 zinc Substances 0.000 claims description 118
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 84
- 229910052725 zinc Inorganic materials 0.000 claims description 84
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- 238000006243 chemical reaction Methods 0.000 claims description 30
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- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
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- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
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- 150000003751 zinc Chemical class 0.000 description 3
- -1 4-cyano-4- [ (dodecylsulfanylsulfanyl) sulfanyl ] pentanoic acid Chemical compound 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
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- 206010014415 Electrolyte depletion Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application provides a preparation method of a high-molecular functional coating for a metal negative electrode. The preparation method comprises the following steps: (1) preparation of a homopolymer containing pyridine ligand groups; (2) modification of the metal negative electrode by the macromolecule coating; (3) The quaternization post-treatment regulates the force between the coordinating groups and the metal ions. The application provides good electrolyte wettability for the coating by utilizing the side chain containing pyridine groups in the homopolymer, and the pyridine groups and Zn 2+ Coordination therebetween slows the corrosion rate of the metal electrode and successfully inhibits dendrite growth and byproduct generation. The application enables the acting force between the coordination group and the metal ion to be adjustable and controllable through quaternization post-treatment, thereby optimizing the multiplying power performance and the cycle performance of the battery.
Description
Technical Field
The application relates to the technical field of new energy materials, in particular to a preparation method and application of a polymer protective layer, and especially relates to a preparation method of a polymer functional coating for a metal negative electrode.
Background
In recent years, the large-scale energy storage has higher requirements on safety, economy and environmental protection, and a series of water-based metal ions (K + 、Zn 2+ 、Na + 、Ca 2+ 、Mg 2+ 、Al 3+ 、Li + ) The energy storage battery gradually reflects into the eye curtain. Wherein, the metallic zinc has 820mAh g -1 Is considered to be an ideal negative electrode material, for example, in terms of high theoretical specific capacity, suitable redox potential (-0.76V vs. standard hydrogen electrode), low cost, etc. However, weak acid ZnSO is currently in common use 4 The electrolyte has higher proton activity than the alkaline electrolyte and thus the thermodynamic tendency of the Hydrogen Evolution Reaction (HER) is stronger. Zinc dendrite growth, continued corrosion of the zinc plates, and accumulation of HER byproducts all reduce cell performance. Therefore, the protection of the zinc cathode can effectively relieve the failure of the battery and is hopeful to avoid potential safety hazards, and the practical process of the water-based zinc ion battery is accelerated.
Various strategies to inhibit dendrite growth and extend cycling performance were compared: various electrolyte additives such as triethyl phosphate, sodium glutamate, etc. have been used to inhibit HER, and although this has proven to be effective, electrolyte depletion occurs after long-term cycling; strategy for optimizing the electrolyte with high concentration of triflate is too costly to be suitable for large scale implementation; whereas alloying of zinc reduces the average capacity due to the introduction of inert metals. In contrast, a functional surface protective layer (e.g., al 2 O 3 、TiO 2 、ZrO 2 Carbon materials, polymers, etc.) can modify the surface of the metal electrode to induce uniform nucleation. Wherein the polymer selected to have a suitable functional group (e.g., a pyridine group) can inhibit Zn by complexation 2+ Is considered as a strategy that can significantly improve the durability of zinc negative electrodes. However, the interfacial resistance and kinetic properties of the polymer coating need to be considered simultaneously.
The present application has been made for the above reasons.
Disclosure of Invention
The application aims at solving the problems pointed out in the background art and the defects of the prior art and provides a preparation method of a polymer coating for a metal negative electrode, wherein a side chain containing pyridine groups provides good electrolyte wettability for the coating and is used for preparing a metal negative electrode by combining Zn with the polymer coating 2+ Coordination between the metal electrodes slows down the corrosion rate of the metal electrodes and inhibits dendrite growthLong. The preparation method is simple to operate, the polymerization degree of the coating can be regulated and controlled, and the obtained product can be subjected to post-modification to regulate and control the acting force between the coordination group and the metal ion.
The application aims at realizing the following technical scheme:
the application provides a preparation method of a high-molecular functional coating for a metal negative electrode, which comprises the following steps:
(1) Preparation of homopolymers containing pyridine ligand groups
Mixing 2-vinyl pyridine monomer, azo initiator, initiation transfer terminator and solvent a for reaction, and adding precipitant b to obtain precipitate polymer, namely poly 2-vinyl pyridine homopolymer (P2 VP);
or mixing 2-vinyl pyridine monomer, azo initiator, initiation transfer terminator and solvent a for reaction, and adding precipitant b to obtain precipitate polymer (poly 2-vinyl pyridine homopolymer P2 VP); dissolving a precipitation polymer in a solvent c, and carrying out quaternization reaction on nitrogen atoms on pyridine rings by utilizing halogenated alkane, and precipitating a precipitation product to obtain quaternary ammonium salt with organic cations and anions on side chains;
(2) Modification of polymer coating to metal negative electrode
And (3) dissolving the poly (2-vinylpyridine) homopolymer or the quaternary ammonium salt obtained in the step (1) in a mixed solvent c to prepare a mixed solution, uniformly coating the mixed solution on the pretreated metal sheet, and drying at a high temperature to obtain the polymer coating modified metal anode containing the coordination group.
Preferably, the azo initiator in the step (1) is used in an amount of 0.01 to 0.05wt% based on the monomer 2-vinylpyridine, and the azo initiator comprises one of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
Preferably, the amount of the initiating transfer terminator in step (1) is 0.1 to 0.5wt% of the monomer 2-vinylpyridine. The initiation transfer terminator includes 4-cyano-4- [ (dodecylsulfanylsulfanyl) sulfanyl ] pentanoic acid.
Preferably, the solvent a in the step (1) comprises one of 1, 4-dioxane and diethyl ether; the precipitant b comprises one of cyclohexane and n-hexane; solvent c comprises one of acetonitrile, ethyl acetate, isopropanol. The dosage ratio of the solvent a to the 2-vinyl pyridine monomer is 20-50 mL:20g. The dosage ratio of the solvent c to the precipitated polymer is 20-40 mL:300mg.
Preferably, the temperature of the mixing reaction in the step (1) is 65-85 ℃, and the reaction time is 2-50 h. The application prepares a reversible addition-fragmentation chain transfer free Radical (RAFT) polymerization reaction system from 2-vinyl pyridine monomer, azo initiator, initiating transfer terminator and solvent a.
Preferably, the reaction is carried out under anhydrous and anaerobic conditions. The precipitated polymer was repeatedly washed with tetrahydrofuran, filtered and dried in vacuo. The temperature of vacuum drying is 60-80 ℃ and the time is 12-24 h.
Preferably, the product poly 2-vinylpyridine homopolymer of step (1) has a molecular weight Mn of 7381 to 44617, comprising P2VP 70 、P2VP 130 、P2VP 209 、P2VP 313 、P2VP 424 The subscript represents the degree of polymerization. Commercially available poly-2-vinylpyridines such as Sigma, fluka, polymer source brands vary in selling price from 1000 to 4000 per gram. The application synthesizes the polymer with controllable molecular weight and smaller polydispersity index by using 2-vinyl pyridine as the monomer RAFT, and has low cost and simple operation. The regulation and control of the molecular weight are mainly controlled by the reaction time. The RAFT reaction system is characterized by controllable structure and lower polydispersity index.
Preferably, the halogenated alkane in the step (1) comprises one of n-bromooctane, bromohexane and chloroform. The dosage ratio of the halogenated alkane to the precipitated polymer is 2-5 mL:300mg.
Preferably, the temperature of the quaternization reaction in the step (1) is 60-80 ℃, the reaction time is 5-200 h, and the quaternization degree is 3-20%. And (3) precipitating and separating out the quaternized material in diethyl ether, repeatedly cleaning with DMF, and vacuum drying the obtained product for 24 hours at 70 ℃ to obtain the quaternary ammonium salt with organic cations and anions on the side chains. The application regulates and controls the acting force between the coordination group and the metal ion through quaternization post-treatment, so as to weaken the coordination effect between the pyridine group and the metal cation and optimize the battery performance. The quaternization degree increases with the extension of the reaction time, and the better the improvement of the quaternization degree is in terms of the experimental results.
Preferably, in the step (2), the mixed solvent c is a mixed solution of tetrahydrofuran and N, N-dimethylformamide, and the volume ratio is 2-6: 1. the concentration of the mixed solution is 2-8 mg mL -1 . The solubility of the P2VP in the THF/DMF mixed solvent is better, the later coating is facilitated, and the coating is more uniform.
Preferably, the high-temperature drying temperature is 60-80 ℃, and the reaction time is 1-3 h.
Preferably, the metal sheet in step (2) comprises one of zinc sheet, aluminum sheet, magnesium sheet. The metal sheet may be extended to other metal electrodes that need protection. The thickness of the metal sheet is 50-100 mu m, and the pretreatment process is to sequentially polish the metal sheet by using 1000-mesh, 2000-mesh, 3000-mesh and 5000-mesh sand paper until the surface is bright and clean.
Preferably, the mixed solution of the metal sheet in the step (2) is coated in an amount of 10 to 30 mu L cm -2 。
The application provides an application of a metal negative electrode prepared by the method in preparation of a water-based zinc ion battery. The corrosion mechanism and dendrite generation induction cause of the conventional lithium metal battery and the water-based zinc ion battery are essentially different, the challenge of lithium metal protection is to regulate uniform deposition of lithium ions, and the challenge of zinc negative electrode protection is to inhibit SO in zinc ions and water-based electrolyte more 4 2- 、OH - By-products of hydration. The poly-2-vinylpyridine coating inhibits zinc ion hydration by chemical complexation to form a uniform zinc layer on the surface, thereby minimizing the concentration gradient at the electrode/electrolyte interface and thus inhibiting dendrite formation. The coating of an aqueous battery needs to have hydrophilicity so as to be stably present in an aqueous medium.
In the prior art, the ionic liquid and the organic solvent are mixed and then coated on the electrode, so that the ionic liquid can only be used in a battery adopting a solid electrolyte, and the ionic liquid has liquid characteristics, unlike a polymer which can form a stable film on the electrode plate after being coated, the film formed by the ionic liquid cannot exist stably in the liquid electrolyte.
Compared with the prior art, the application has the following beneficial effects:
(1) The application provides good electrolyte wettability for the coating by utilizing the side chain containing pyridine groups in the homopolymer, ensures smooth passage of ions between electrode interfaces, reduces interface resistance between the coating and the pole piece, and ensures stable reaction kinetics.
(2) The application utilizes pyridine groups and Zn 2+ The coordination between the metal electrodes slows down the corrosion rate of the metal electrodes, remarkably widens the corrosion potential of the electrodes, has lower corrosion current, and successfully inhibits the growth of dendrites and the generation of byproducts.
(3) The application adjusts the quaternization degree of the product through quaternization post-treatment so that the acting force between the coordination group and the metal ion can be regulated and controlled. The barrier effect of the coating on zinc ion diffusion is further slowed down by shielding the strong coordination of a part of pyridine groups on metal ions, and the rate capability and the cycle performance of the battery are optimized.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is an SEM photograph of (a and c) blank zinc sheets and (b and d) zinc anodes with P2VP coating modification as described in example 1, before and after soaking in a zinc ion-containing electrolyte;
FIG. 2 is a graph showing the N1s XPS spectra of (a) zinc anodes with P2VP and P4VP coating modifications as described in example 1 and (b) comparative example 2, before and after immersion in zinc ion containing electrolyte;
FIG. 3 is an SEM photograph of a zinc-symmetric cell assembled with zinc anode modified with P2VP and P4VP coatings after 50 hours of cycling using (a) blank zinc sheets, (b) example 2, (c) comparative example 1, and (d) comparative example 2;
FIG. 4 is a zinc anode package with P2VP and quaternized P2VP coating finishes as described in example 2 and example 6The prepared zinc symmetric battery is 0.2-10 mA cm -2 Rate capability at current density;
FIG. 5 is a graph showing the cycling performance of an aqueous zinc ion cell assembled using a zinc anode with a quaternized P2VP coating modification and a bare zinc sheet as described in example 6;
fig. 6 (a and c) SEM photographs of the zinc anode with PS and P4VP coating modifications described in comparative example 1 and (b and d) comparative example 2 before and after soaking in the zinc ion-containing electrolyte.
Detailed Description
The application is described in further detail below with reference to the drawings and examples. The present embodiment is implemented on the premise of the present technology, and a detailed embodiment and a specific operation procedure are now given to illustrate the inventive aspects of the present application, but the scope of protection of the present application is not limited to the following embodiments. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present application.
Example 1
In this embodiment, there is provided a method for preparing a polymer coating layer containing pyridine ligand group for a metal anode, the method comprising:
preparing a RAFT reaction system: 20g of 2-vinylpyridine monomer, 2mg of Azobisisobutyronitrile (AIBN) initiator, 20mg of 4-cyano-4 [ (dodecylsulfanylthiocarbonyl) sulfanyl ] are weighed out]Valeric acid (CDPA) initiated transfer terminator, and 20mL 1, 4-dioxane solvent were added to a 100mL flask, and the solution was bubbled for half an hour to remove oxygen therefrom, and the solution was sufficiently dissolved by magnetic stirring. And (3) vacuumizing, recharging nitrogen for protection, and carrying out polymerization reaction for 2 hours at 65 ℃, wherein the mixed solution gradually becomes viscous along with the progress of the reaction. After the reaction, the obtained viscous solution was precipitated with a cyclohexane precipitant, and the precipitate was repeatedly washed with Tetrahydrofuran (THF). Finally, the precipitate is put into a vacuum oven to be dried for 12 hours at 60 ℃ to obtain P2VP 70 (molecular weight Mn is 7381).
Pretreatment of the zinc cathode: a50 μm thick zinc sheet (99.9%) was successively sanded with 1000 mesh, 2000 mesh, 3000 mesh, 5000 mesh sandpaper to a bright and clean surface.
Modification of a metal negative electrode by a high polymer coating: adding the dried P2VP into THF and N, N-Dimethylformamide (DMF) in a volume ratio of 2:1 is configured to have a concentration of 2mg mL -1 P2VP solution of (2), then according to 10. Mu.L cm -2 Uniformly coating the P2VP solution on the surface of the pretreated zinc sheet, then drying at 60 ℃ for 1h, and cutting the zinc sheet coated with the polymer protective layer into electrode sheets with the diameter of 12mm for standby.
The applicant carried out a microscopic examination of the obtained zinc anode with the P2VP coating modification to obtain a scanning electron micrograph shown in fig. 1. As shown in fig. 1a and b, the P2VP-Zn in this example had a smooth and even surface compared to crisscrossed scratches on a blank Zn sheet. At this time, the polymer coating can exert the ductility advantage thereof, spread on the surface of the zinc sheet, fill up pits and scratches of the zinc sheet, which is favorable for the construction of stable interfaces.
The thermodynamic instability of zinc cathodes in weakly acidic electrolytes can lead to their corrosion/passivation also in the rest state, i.e. the zinc cathodes become progressively weaker and even fail, which is a typical scenario in practical applications. To simulate this use scenario, the applicant further soaked Zn, P2VP-Zn in a solution containing Zn 2+ Seven days in the electrolyte of (2) and compares the state of the cathodes before and after soaking. As shown in FIGS. 1c and d, the surface of the zinc sheet is severely corroded after immersing the electrolyte, and a large number of irregular sheets appear, which is Zn 2+ Is a hydration product of (a) a catalyst. This corrosion was significantly improved when the zinc sheet was protected by the P2VP coating, and no significant platelet accumulation was observed.
The applicant further performs Zn soaking 2+ XPS test is carried out on the zinc anode with P2VP coating modification before and after the electrolyte, and the P2VP and Zn are verified 2+ Coordination between them. As can be seen from the N1s XPS spectrum 2a of the P2VP, the binding energy of nitrogen element corresponding to the P2VP is shifted by 0.85eV towards the high binding energy before and after the electrolyte is soaked, which shows that the pyridine nitrogen and Zn 2+ A certain degree of coordination takes place between them. P2VP has larger spatial bitsResistance to Zn 2+ Coordination is hindered by the backbone and does not tend to form further three-dimensional structures, which is consistent with SEM results.
Example 2
In this embodiment, there is also provided a method for producing a pyridine ligand group-containing polymer coating for a metal anode, the method comprising:
preparing a RAFT reaction system: 20g of 2-vinylpyridine monomer, 4mg of Azobisisoheptonitrile (ABVN) initiator, 40mg of CDPA-initiated transfer terminator, and 30mL of diethyl ether solvent were weighed into a 100mL flask, and oxygen in the solution was purged by bubbling for half an hour, followed by magnetic stirring to dissolve it sufficiently. And (3) vacuumizing, recharging nitrogen for protection, and carrying out polymerization reaction for 8 hours at 70 ℃, wherein the mixed solution gradually becomes viscous along with the progress of the reaction. After the reaction, the obtained viscous solution was precipitated with a normal hexane precipitant, and the precipitate was repeatedly washed with Tetrahydrofuran (THF). Finally, the precipitate is put into a vacuum oven to be dried for 18 hours at 70 ℃ to obtain P2VP 209 (molecular weight Mn is 21985).
Modification of a metal negative electrode by a high polymer coating: adding the dried P2VP into THF and DMF with the volume ratio of 4:1 in a concentration of 4mg L -1 P2VP solution of (2), then according to 20. Mu.L cm -2 Uniformly coating the P2VP solution on the surface of the pretreated zinc sheet, then drying at 70 ℃ for 2 hours, and cutting the zinc sheet coated with the polymer protective layer into electrode sheets with the diameter of 12mm for standby.
The applicant further assembled the zinc anode with the P2VP coating modification described in this example into a Zn symmetric battery for constant current (1 mA cm -2 ) And (3) carrying out a cycle test for 50 hours, and after the cycle is finished, disassembling the button cell, taking out the P2VP-Zn after the cycle, and carrying out SEM (scanning electron microscope) detection to evaluate the dendrite inhibition capability of the coating. As shown in fig. 3a and b, the surface of the blank zinc sheet after circulation has more flaky byproducts and irregular particle dendrite aggregation, reflecting unstable deposition and stripping of the electrode in circulation. Whereas the surface of the zinc anode with the P2VP coating modification was flat and no significant zinc dendrite formation was observed, indicating that the P2VP coating resulted in ion transfer at the zinc anode surfaceMore orderly, and improves the stability of the circulation.
Example 3
In this embodiment, there is also provided a method for producing a pyridine ligand group-containing polymer coating for a metal anode, the method comprising:
preparing a RAFT reaction system: 20g of 2-vinylpyridine monomer, 10mg of Azobisisoheptonitrile (ABVN) initiator, 100mg of CDPA initiated transfer terminator, and 40mL of 1, 4-dioxane solvent were weighed into a 100mL flask, and oxygen in the solution was purged by bubbling for half an hour, followed by magnetic stirring to dissolve it sufficiently. And (3) vacuumizing, recharging nitrogen for protection, and carrying out polymerization reaction for 50 hours at the temperature of 85 ℃, wherein the mixed solution gradually becomes viscous along with the progress of the reaction. After the reaction, the obtained viscous solution was precipitated with a cyclohexane precipitant, and the precipitate was repeatedly washed with Tetrahydrofuran (THF). Finally, the precipitate is put into a vacuum oven to be dried for 24 hours at the temperature of 80 ℃ to obtain P2VP 424 (molecular weight Mn is 44617).
Modification of a metal negative electrode by a high polymer coating: the dried P2VP is added into THF and DMF with the volume ratio of 6:1 is prepared into a concentration of 8mg L -1 P2VP solution of (C) and then was applied at 30. Mu.L cm -2 Uniformly coating the P2VP solution on the surface of the pretreated zinc sheet, then drying at 80 ℃ for 3 hours, and cutting the zinc sheet coated with the polymer protective layer into electrode sheets with the diameter of 12mm for standby.
Example 4
In this embodiment, a method for preparing a reaction force between a quaternized post-treatment regulatory ligand group and a metal ion is provided, the method comprising:
300mg of the P2VP powder described in example 1 was dissolved in 20mL of acetonitrile, 2mL of chloroform was added, the reaction was carried out at 60℃for 5 hours, and after completion of the reaction, the quaternized material was precipitated in diethyl ether and repeatedly washed with DMF. The resulting product was vacuum dried at 70℃for 24h. The dried quaternized P2VP was added to THF and DMF at a volume ratio of 2:1 is prepared into a concentration of 2mg L -1 Cl-P2VP solution of (C) and then was applied at 10. Mu.L cm -2 Coating amount of (C) Cl-PThe 2VP solution is uniformly coated on the surface of the pretreated zinc sheet, and then the zinc sheet coated with the polymer protective layer is dried for 1h at 60 ℃ and cut into electrode sheets with the diameter of 12mm for standby.
Example 5
In this embodiment, there is also provided a method for preparing a reaction force between a quaternized post-treatment regulatory ligand group and a metal ion, the method comprising:
300mg of the P2VP powder described in example 2 was dissolved in 30mL of acetonitrile, 4mL of n-bromooctane was added, the reaction was carried out at 70℃for 50 hours, after the completion of the reaction, the quaternized material was precipitated in diethyl ether and washed repeatedly with DMF. The resulting product was vacuum dried at 70℃for 24h. The dried quaternized P2VP was added to THF and DMF at a volume ratio of 4:1 in a concentration of 4mg L -1 Br-P2VP solution of (B), then at 20. Mu.L cm -2 Uniformly coating Br-P2VP solution on the surface of the pretreated zinc sheet, then drying at 70 ℃ for 2 hours, and cutting the zinc sheet coated with the polymer protective layer into electrode sheets with the diameter of 12mm for standby.
Example 6
In this embodiment, there is also provided a method for preparing a reaction force between a quaternized post-treatment regulatory ligand group and a metal ion, the method comprising:
300mg of the P2VP powder described in example 3 was dissolved in 40mL of acetonitrile, 5mL of bromohexane was added, the reaction was carried out at 80℃for 200 hours, after the reaction was completed, the quaternized material was precipitated in diethyl ether and repeatedly washed with DMF. The resulting product was vacuum dried at 70℃for 24h. The dried quaternized P2VP was added to THF and DMF at a volume ratio of 6:1 is prepared into a concentration of 8mg L -1 Cl-P2VP solution of (C) and then was applied at 30. Mu.L cm -2 Uniformly coating Br-P2VP solution on the surface of the pretreated zinc sheet, then drying at 80 ℃ for 3 hours, and cutting the zinc sheet coated with the polymer protective layer into electrode sheets with the diameter of 12mm for standby.
Applicants further carried out the process described in example 2 and this example with P2VP and quaternized P2Assembling the VP coating modified zinc cathode into a Zn symmetric battery for 0.2-10 mA cm -2 The current density of (2) was evaluated for high current density resistance by quaternizing P2VP to a zinc anode, and the test results are shown in fig. 4. It can be seen that the Br-P2VP coated zinc flake has a lower deposition potential than the P2VP coated zinc flake, and a current density tolerance of greater than 10mA cm -2 。
The applicant further assembled the zinc negative electrode with the quaternized P2VP coating modification and the vanadium oxide positive electrode described in this example into an aqueous zinc ion battery. Preparation of vanadium oxide positive electrode: 0.25g of ammonium vanadate (NH) 4 VO 3 ) Adding into 15mL deionized water, stirring to dissolve, and adding phosphoric acid (H) 3 PO 4 88%) to a PH of 2.0, at which time the color of the solution changed from clear to reddish wine. The solution was transferred to a reaction vessel and reacted at 180℃for 24 hours. After the reaction was completed, the precipitate was centrifugally washed with deionized water and then dried at 100℃for 24 hours. The prepared (NH) 4 ) 2 V 6 O 16 ·1.5H 2 O powder and acetylene black, polyvinylidene fluoride (PVDF) powder according to 7:2:1, dropwise adding a proper amount of N-methyl pyrrolidone (NMP), ball milling for 2 hours until the slurry is uniformly mixed. The slurry is uniformly coated on titanium foil with the thickness of 20 mu m by a scraper, and is dried for 24 hours in a vacuum oven at 80 ℃ and cut into pieces to obtain the vanadium oxide anode. Electrochemical performance testing was performed to obtain rate capability and FIG. 5 at 1A g -1 Cycling stability at current density. Battery at 0.2A g -1 Exhibits 334.7mAh g -1 High initial discharge capacity of (a). Even at 5A g -1 Still having 99.2mAh g at high current density -1 Is a function of the capacity of the battery. Besides excellent multiplying power performance, the cycle stability of the battery is greatly improved compared with that of a water-based zinc ion battery assembled by blank zinc sheets, and the battery is 1A g -1 The capacity after the lower circulation exceeds 300 circles is 263.1mAh g -1 The capacity fade is very small.
Example 7
This embodiment is substantially the same as embodiment 1, except that: the reaction time of the 2-vinyl pyridine monomer is 4h, and the obtainedThe product of (2) is P2VP 130 (molecular weight Mn is 13674).
Example 8
This embodiment is substantially the same as embodiment 1, except that: the reaction time of the 2-vinyl pyridine monomer is 24h, and the obtained product is P2VP 313 (molecular weight Mn is 32893).
Example 9
This comparative example is substantially identical to example 5, except that: the quaternization reaction time is 10h.
Example 10
This comparative example is substantially identical to example 5, except that: the quaternization reaction time was 24h.
Comparative example 1
In this comparative example, there is provided a method for producing a polymer coating layer for a metal anode, which does not contain a coordinating group, the method comprising:
modification of a metal negative electrode by a high polymer coating: polystyrene (PS) was added to THF and DMF at a volume ratio of 4:1 in a concentration of 4mg L -1 PS solution of (C) and then according to 10. Mu.L cm -2 The PS solution was uniformly coated on the surface of the pretreated zinc sheet (the pretreatment of the zinc anode was the same as in example 1), followed by drying at 60℃for 1 hour, and the zinc sheet coated with the polymer protective layer was cut into electrode sheets having a diameter of 12mm for use.
The applicant carried out a microscopic examination of the obtained zinc anode with PS coating modification to obtain a scanning electron micrograph shown in fig. 1 c. As shown in fig. 1c, the PS-coated modified zinc sheet surface described in this comparative example has a discontinuous porous structure, probably due to rapid evaporation of the solvent and shrinkage of the material.
The applicant further carried out the PS-coated modified zinc anode described in this comparative example on a zinc-containing substrate 2+ And (3) soaking in the electrolyte for 7 days, and then performing scanning electron microscope detection again to compare the corrosion resistance of the PS coating. As shown in FIGS. 6a and c, after PS is immersed in the electrolyte, PS-Zn has no obvious difference before the surface morphology of the zinc sheet is immersed due to the hydrophobicity of PS. This illustrates the lack of sidesPyridine groups on the chain, the electrolyte becomes difficult to reach the pole piece surface, which is very detrimental to the reaction kinetics.
The applicant further assembled the zinc anode with PS coating modification described in this comparative example into a Zn symmetric battery for constant current (1 mA cm -2 ) And (3) carrying out a cycle test for 50 hours, and after the cycle is finished, disassembling the button cell, taking out the PS-Zn after the cycle, and carrying out SEM (scanning electron microscope) detection to evaluate the dendrite inhibition capability of the coating. As shown in FIG. 3c, the PS-Zn surface after cycling presents a large number of bulk stacks, which are related to its poor electrolyte wettability.
Comparative example 2
In this comparative example, there is also provided a method for producing a pyridine ligand group-containing polymer coating for a metal anode, the method comprising:
modification of a metal negative electrode by a high polymer coating: poly 4-vinylpyridine (P4 VP) (commercially available, molecular weight 60000, degree of polymerization 571) was added to a volume ratio of THF to DMF of 4:1 in a concentration of 4mg L -1 PS solution of (C) and then according to 10. Mu.L cm -2 The P4VP solution was uniformly coated on the surface of the pretreated zinc sheet (the pretreatment of the zinc cathode was the same as in example 1), followed by drying at 60℃for 1 hour, and the zinc sheet coated with the polymer protective layer was cut into electrode sheets having a diameter of 12mm for use.
The applicant carried out a microscopic examination of the obtained zinc anode with the P4VP coating modification to obtain a scanning electron micrograph shown in fig. 6 b. As shown in fig. 6b, the P4 VP-coated zinc sheet described in the present comparative example has an improved surface flatness compared to a blank zinc sheet, but there is still a scratch structure that can be seen, and there is a small amount of agglomeration of P4 VP.
The applicant further modified the zinc anode with P4VP coating described in this comparative example in a Zn-containing state 2+ And (3) soaking in the electrolyte for 7 days, and then performing scanning electron microscope detection again to compare the corrosion resistance of the P4VP coating. As shown in fig. 6d, after the zinc sheet coated with P4VP is immersed in the electrolyte, the surface has serious particle aggregation and uneven dispersion.
Applicant furtherTo soak Zn 2+ XPS test is carried out on the zinc anode with P4VP coating modification before and after electrolyte, and the P4VP and Zn are verified 2+ Coordination between them. As can be seen in the N1s XPS spectrum 2b of the P4VP, the binding energy of nitrogen element corresponding to the P4VP is shifted by 1.59eV towards the high binding energy direction before and after the electrolyte is soaked, and the shift of the higher energy indicates that the pyridine nitrogen and Zn in the P4VP molecule 2+ The coordination between the two is stronger than that of P2VP. It is this strong complexation with low steric hindrance that induces further aggregation of the byproducts, which is consistent with SEM results.
The applicant further assembled the zinc anode with the P4VP coating modification described in this comparative example into a Zn symmetric battery for constant current (1 mA cm -2 ) And (3) carrying out a cycle test for 50 hours, and after the cycle is finished, disassembling the button cell, taking out the cycled P4VP-Zn, and carrying out SEM (scanning electron microscope) detection to evaluate the dendrite inhibition capability of the coating. As shown in fig. 3d, the coating of P4VP, while inhibiting zinc dendrite formation, can inhibit charge transfer at the electrode surface due to by-product reagglomeration induced by its strong complexation, thereby reducing cycling stability.
Verification embodiment
In this example, the P2VP described in examples 1 to 3 and examples 7 to 8 was first subjected to Gel Permeation Chromatography (GPC) test and a zinc anode with P2VP coating modification was assembled into a Zn symmetric cell for constant current (1 mA cm) -2 ) The following long-cycle stability test gave the test results shown in table 1. P2VP with different polymerization degrees can be obtained by regulating the reaction time (2-50 h), so that the protection effect of the P2VP coating on the zinc cathode is optimized.
TABLE 1 Regulation of degree of polymerization for Zinc cathode protection
Further, the applicant conducted contact angle tests on zinc cathodes with P2VP, PS and P4VP coating modifications described in example 2 and comparative examples 1-2, and the results are listed in table 2. Compared with blank zinc sheets, the zinc sheets coated with the P2VP and the P4VP have better wettability to electrolyte, and the corresponding contact angles are 66.5 degrees and 54.0 degrees respectively. In addition, the contact angles of the electrolyte on Zn, P2VP-Zn and P4VP-Zn surfaces gradually decrease with time. In contrast to the PS-coated zinc sheet, the contact angle of the electrolyte on the surface of the sheet does not decrease with time, which indicates that the PS-coated layer has poor wettability with respect to the electrolyte, and the poor wettability is unfavorable for mass transfer between electrode interfaces.
Further, the applicant assembled zinc cathodes with P2VP, PS and P4VP coating modifications described in example 2 and comparative examples 1-2 into Zn Ti asymmetric cells and Zn symmetric cells for long-cycle stability test and impedance test under constant current, and the detection results are shown in table 2. It can be seen that zinc anodes with P2VP coating modifications have higher coulombic efficiency, lower charge transfer resistance, and longer stable voltage duration.
TABLE 2 comparison of Zinc cathode Performance with P2VP, PS and P4VP coating modifications
Further, the quaternized P2VP described in examples 4 to 6 and examples 9 to 10 was subjected to nuclear magnetic resonance hydrogen spectroscopy 1 H NMR) analysis the quaternization degree of the product calculated by the integral area of the characteristic peaks, and assembling a zinc anode with the quaternization P2VP coating modification into a Zn symmetric battery for high current density (10 mA cm) -2 ) The following long-cycle stability test gave the test results shown in table 3. P2VP with different quaternization degrees can be obtained by regulating and controlling the reaction time (5-200 h), so that acting force between the coordination group and the metal ion is regulated and controlled, and the protection effect of the coating on the zinc cathode is further optimized.
TABLE 3 Regulation of the degree of quaternization on the protection of zinc cathodes
The foregoing describes specific embodiments of the present application. It is to be understood that the application is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the application.
Claims (8)
1. The application of the metal negative electrode in preparing the water-based zinc ion battery is characterized in that the preparation method of the metal negative electrode comprises the following steps:
(1) Preparation of quaternary ammonium salts
Mixing 2-vinyl pyridine monomer, azo initiator, initiation transfer terminator and solvent a for reaction, and adding precipitant b to obtain precipitate polymer; dissolving a precipitation polymer in a solvent c, and carrying out quaternization reaction on nitrogen atoms on pyridine rings by utilizing halogenated alkane, and precipitating a precipitation product to obtain quaternary ammonium salt with organic cations and anions on side chains;
(2) Modification of polymer coating to metal negative electrode
Dissolving the quaternary ammonium salt obtained in the step (1) in a mixed solvent to prepare a mixed solution, uniformly coating the mixed solution on the pretreated metal sheet, and drying at high temperature to obtain a metal anode modified by a polymer coating containing a coordination group;
in the step (2), the metal sheet is a zinc sheet.
2. The use according to claim 1, wherein the azo initiator in step (1) is used in an amount of 0.01 to 0.05wt% of the 2-vinylpyridine monomer, and the azo initiator comprises one of azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate.
3. The use according to claim 1, wherein the amount of the transfer initiator used in step (1) is 0.1 to 0.5 wt.% of the monomeric 2-vinylpyridine.
4. The use according to claim 1, wherein the solvent a in step (1) comprises one of 1, 4-dioxane, diethyl ether; the precipitant b comprises one of cyclohexane and n-hexane.
5. The use according to claim 1, wherein the temperature of the mixing reaction in step (1) is 65-85 ℃ and the reaction time is 2-50 hours.
6. The use according to claim 1, wherein the haloalkane in step (1) comprises one of n-bromooctane, bromohexane, chloroform.
7. The use according to claim 1, wherein the quaternization reaction in step (1) is carried out at a temperature of 60 to 80 ℃ for a period of 5 to 200 hours.
8. The application of claim 1, wherein in the step (2), the mixed solvent is a mixed solution of tetrahydrofuran and N, N-dimethylformamide, and the volume ratio is 2-6: 1.
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