CN114552029A - Zeolite-based ion exchange coating for long-life zinc-iodine battery - Google Patents
Zeolite-based ion exchange coating for long-life zinc-iodine battery Download PDFInfo
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Classifications
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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
- H01M10/365—Zinc-halogen accumulators
-
- 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
- H01M10/38—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a zeolite-based ion exchange coating for a long-life zinc-iodine battery, which comprises a zeolite material and a binder, wherein the average particle size of the zeolite material is not more than 100 mu m; when the zeolite-based ion exchange coating is applied to a zinc-iodine battery, the zeolite-based ion exchange coating is attached to the surface of a zinc cathode or a battery diaphragm; can block I3 ‑The ion shuttling, the growth inhibition of dendrites and the corrosion of the electrolyte to the zinc cathode. The invention also discloses a long-life zinc-iodine battery comprising the zeolite-based ion exchange coating. The coating is cheap, light and pollution-free, can be continuously produced on the existing battery coating equipment, does not influence the assembly process of the original secondary zinc-iodine battery, does not remarkably reduce the energy density and the power density of the secondary zinc-iodine battery, and can remarkably improve the performance of the secondary zinc-iodine batteryThe cycle life is suitable for all zinc-iodine battery systems.
Description
Technical Field
The invention belongs to the field of secondary batteries, and particularly relates to a zeolite-based ion exchange coating for a long-life zinc-iodine battery.
Background
The rechargeable battery (secondary battery) is a core device for driving electric vehicles, mobile electronic terminals and smart grids. However, currently widely used lithium batteries use ester or ether organic electrolytes, which present a combustion hazard during abuse. The lead-acid battery using the water system electrolyte has high safety and cost performance, but the energy density and the cycle life are not satisfactory; in addition, the use of lead elements with high pollution also brings certain pollution hidden trouble. Therefore, there is an urgent need to develop a green rechargeable battery system with high performance, low cost and high safety.
The rechargeable zinc-iodine battery (hereinafter referred to as zinc-iodine battery) takes elemental iodine with high capacity and high potential difference and metal zinc as a positive electrode and a negative electrode, the two electrodes store charges through a unique dissolution-deposition mechanism, and compared with a common ion embedding or conversion reaction mechanism, the rechargeable zinc-iodine battery has the outstanding advantages of high reaction speed, good reversibility, high energy/power density and the like. In addition, the battery system can use a non-flammable zinc salt aqueous solution as an electrolyte, and all components of the battery have the advantages of low cost, high environmental protection, high use safety and the like, so that the battery system has a great development prospect. Both theoretical calculations and experimental studies confirm that zinc-iodine cells are expected to achieve theoretical energy densities (based on electrode material) as high as 310Wh/kg, one of the highest energy density water-based cells.
Although the energy storage reaction mechanism of the zinc-iodine battery is simpler, a plurality of harmful side reaction processes exist, and the improvement of the battery performance is seriously influenced. Firstly, during the charging and discharging process of the battery, I2The positive electrode and its discharge product I-Ion complexation to form soluble I3 -The anions enter the electrolyte causing the loss of the positive electrode material. In the electrolyte I3 -After the zinc oxide migrates to the surface of the negative electrode, the zinc oxide also generates oxidation-reduction reaction with the metal zinc, so that the corrosion of the zinc negative electrode is caused, and a series of problems of self-discharge, capacity attenuation and the like of the battery are caused. The above process is called I3 -The shuttling effect. Secondly, the reaction potential of the metallic zinc is lower than the reduction hydrogen evolution potential of water molecules, so hydrogen evolution corrosion and surface passivation can occur in the electrolyte, and the loss and increase of the negative electrode are causedThe internal resistance of the battery is large. Finally, under the action of a point discharge effect and an uneven passivation layer, the zinc cathode can spontaneously grow large-size zinc dendrites; these zinc dendrites easily pierce the separator, causing short circuit failure of the cell; even before the membrane is pierced, the loose or broken zinc dendrites lose electrical contact with the current collector, turning into "dead zinc" that does not contribute to capacity, causing the cell capacity to fade. These problems are the core problems that plague the performance improvement of zinc-iodine cells.
To inhibit I3 -Shuttle Effect and I2Loss of the positive electrode, researchers propose2Experimental concept of anchoring on porous carrier. For example, Jiangqia and Wangkngli professor team at Huazhong university of science and technology developed the activated carbon-loaded I2 composite cathode material, and examined I2Influence of the load on the cell performance (Journal of Materials Chemistry A2020, 8(7), 3785-3794). In the material, the activated carbon not only can improve the conductivity of the composite electrode, but also can improve I/I-The electrochemical conversion reaction is limited in the pore channels, and the inhibition I is realized through the space confinement effect3 -And the shuttling effect improves the coulombic efficiency and the cycle life of the battery. I is directly combined by a Chunshizi professor team of hong Kong City university through an electrodeposition method2Active material is deposited in accordion-shaped Mxene nanosheet array, the high conductivity of MXene is utilized to optimize the reaction kinetic process of the battery, and the surface functional group of MXene is utilized to adsorb I3 -Shuttle effects are suppressed (Advanced Materials 2021,33(8), 2006897). In addition, the group also developed iodine/Prussian blue analogue composite electrodes by combining I2The molecules are filled into the ordered lattice pore canal of the Prussian blue analogue to realize the I of the molecular level2Limit the range and enhance I2And the host crystal lattice synchronously inhibit I3 -Generation and migration (Angewandte Chemie International Edition 2020,60(7), 3791-. More importantly, the transition metal element in the Prussian blue analogue can also accelerate I/I through electrocatalytic effect-And (4) conversion reaction of the electricity pair.
In addition to the design of the anode material, between the anode and the cathodeBy providing an anion selective barrier, I can also be effectively inhibited3 -Shuttling effect of ions. In the fields of batteries and chemical industry, a Nafion cation exchange membrane is the most widely applied anion selective barrier material at present, and the high density-SO on the main chain of the Nafion cation exchange membrane3 2-The functional group inhibits anion migration by electrostatic repulsion, thereby forming a cation specific channel (Energy)&Environmental Science 2017,10(3), 735-741). However, Nafion membranes are expensive and have much lower ionic conductivity than traditional liquid electrolytes, and therefore Nafion membranes are used to block I in zinc-iodine cells3 -The shuttle effect will significantly reduce the cost advantage and power density of the zinc-iodine cell. The Zhouhaoprudent professor team of Nanjing university proposes selective shielding of I by constructing a Zn-BTC type MOF layer on the surface of a zinc negative electrode3 -Anion, thereby inhibiting the shuttling effect (Advanced Materials 2020,32(38), 2004240). Research shows that COO on the inner wall of Zn-BTC pore channel-The radicals may function like-SO3 2-By selective barrier I by electrostatic repulsion3 -And at the same time ensure Zn2+Smooth and uniform migration of cations. The MOF film can also filter out Zn through desolvation effect2+Loose water molecules in the ion solvation shell layer effectively inhibit harmful processes such as zinc corrosion and zinc dendrite growth. In addition, the surface coating can also act as a physical barrier, further reducing the membrane puncture and cell short circuit probability. In addition, by utilizing the principle of anion selective shielding, gel electrolyte based on alginic acid polyanion is developed, and the gel electrolyte can not only inhibit I3 -The shuttle effect improves the coulombic efficiency and cycle life of the zinc-iodine battery, and can reduce the contact between free water and the zinc cathode, and reduce the zinc corrosion speed (ACS Appl Mater Interfaces 2021,13(21), 24756-24764).
In conclusion, although the performance of the secondary zinc-iodine battery is excellent, no cheap, green and efficient zinc cathode protection method exists at present, and I can be effectively prevented3 -The ion shuttling simultaneously inhibits the corrosion passivation and dendritic crystal growth of the zinc cathode. TheseThe problem is the core problem of limiting the development of the long-life secondary zinc-iodine battery for a long time.
Disclosure of Invention
The invention aims at the defects of the prior art and provides a zeolite-based ion exchange coating for a long-life zinc-iodine battery and a zinc-iodine battery comprising the coating. The coating of the present invention may be used in hindrance I3 -The ion shuttling can inhibit the corrosion passivation of the zinc cathode and the modification of the zinc cathode by dendritic crystal growth, thereby greatly prolonging the cycle life of the zinc-iodine battery.
The specific technical scheme is as follows:
it is an object of the present invention to provide a zeolite-based ion exchange coating for long life zinc-iodine batteries which differs from the prior art by comprising a zeolite material and a binder, said zeolite material having an average particle size of no more than 100 μm;
when the zeolite-based ion exchange coating is applied to a zinc-iodine battery, the zeolite-based ion exchange coating is attached to the surface of a zinc cathode or a battery diaphragm.
The zeolite-based ion exchange coating can be attached to the surface of a zinc cathode or a battery diaphragm, and can also be an independent film coating or a gel/semi-gel composite electrolyte film.
The zeolite-based ion exchange coating of the present invention can hinder I3 -The innovative mechanism and the outstanding technical effect of the ion shuttling and dendritic crystal growth inhibition are as follows:
a) zeolite in zeolite-based ion exchange coating is due to [ SiO ]4]Tetrahedral body [ AlO4]Hexahedral replacement, negatively charged cavities appear in the zeolite, which hinder I by electrostatic interactions3 -The shuttling in the zeolite effectively reduces the self-discharge process of the zinc-iodine battery;
b) the wide and uniform existence of electronegative cavities in zeolite-based ion exchange coatings can guide Zn2+Uniform deposition and avoiding Zn2+As the point discharge accumulates to form dendrites and grow;
c) the zeolite-based ion exchange coating isolates the electrolyte from the zinc cathode, so that the hydrogen evolution reaction of the zinc cathode is avoided, the generation of byproducts is reduced, and the passivation of the zinc cathode is inhibited.
Therefore, the zeolite-based ion exchange coating can effectively block I under the synergistic effect of the three mechanisms3 -The ion shuttling can inhibit the corrosion passivation and dendritic crystal growth of the zinc cathode, thereby greatly prolonging the cycle life of the zinc battery.
The zeolite-based ion exchange coating has the function of a battery diaphragm, and can avoid the use of the battery diaphragm, thereby simplifying the structure and the preparation process of the battery.
Furthermore, the thickness of the zeolite-based ion exchange coating is 0.02-500 mu m.
Further, the zeolite material may be, but is not limited to, natural zeolite and/or artificial zeolite.
Further, the binder is preferably, but not limited to, one or more of Polytetrafluoroethylene (PTFE), Polystyrene (PS), polymethyl methacrylate (PMMA), polyvinylpyrrolidone (PVP), Polyacrylonitrile (PAN), carboxymethyl cellulose (CMC), Styrene Butadiene Rubber (SBR), polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), sodium alginate, polyacrylic acid (PAA), Polyurethane (PU), polyvinyl alcohol (PVA), polyolefins, and fluorinated rubber.
Further, the zeolite material and the binder may be mixed in any ratio. Preferably, the content of zeolite material in the zeolite based ion exchange coating is above 60 wt%.
Further, the zeolite-based ion exchange coating is preferably no more than 15 μm, more preferably no more than 200 nm.
Further, the preparation method of the zeolite-based ion exchange coating comprises the following steps: mixing a zeolite material with a binder to obtain a coating raw material; and coating the coating raw material on the surface of a zinc cathode or a battery diaphragm to obtain the zeolite-based ion exchange coating.
Wherein the coating process is completed by adopting the prior known processes such as blade coating, dip coating, spray coating, roll coating and the like.
Wherein, optionally, after the zeolite-based ion exchange coating is applied, a drying process may be performed.
Wherein, optionally, when the zeolite material is mixed with the binder, a solvent may be added to prepare a slurry-like coating raw material.
Another object of the present invention is to provide a long life zinc-iodine battery comprising the above zeolite-based ion exchange coating.
Further, the long-life zinc-iodine battery comprises a zinc negative electrode or a separator material coated with the zeolite-based ion exchange coating.
The battery diaphragm can adopt the existing known battery diaphragm material, and can be one or more than two of filter paper, non-woven fabric, cellulose membrane, various fiber felts, optical cable paper and organic diaphragm.
Wherein, the zinc negative electrode at least comprises two parts of an active material and a negative current collector; the active substance can be a simple zinc substance, a zinc alloy, or an intermetallic compound of zinc, etc.; the active substance can be loaded on a zinc negative current collector before the battery is assembled, or can be in-situ deposited on the surface of the negative current collector by a battery charging method after the battery is assembled to obtain a negative active substance; the current collector is made of a battery current collector material which is well known in the prior art and can be, but is not limited to, aluminum, copper, stainless steel, carbon or titanium. If a foil-shaped or three-dimensional porous active substance is selected, the active substance can have the function of a current collector, and the active substance and the negative current collector can be combined into a whole.
The invention has the following beneficial effects:
compared with the prior art, the zeolite-based ion exchange coating in the invention can block I3 -Ion shuttling and dendrite growth inhibition; the coating is cheap, light and pollution-free, can be continuously produced on the existing battery coating equipment, does not influence the assembly process of the original secondary zinc-iodine battery, does not remarkably reduce the energy density and the power density of the secondary zinc-iodine battery, can remarkably prolong the cycle life of the secondary zinc-iodine battery, is suitable for all zinc-iodine battery systems, and has great economic and social benefits.
Drawings
FIG. 1 is a schematic view of a liquid crystal display device, each of which is composed ofZinc negative electrode in comparative example 1 and zinc negative electrode immersion I in example 53 -Absorption spectra obtained from the solution;
fig. 2 is a charge-discharge curve of a self-discharge test obtained from the zinc-iodine full cells assembled in comparative example 2 and example 8;
fig. 3 is a comparative graph of cycling stability of a symmetrical zinc/zinc cell assembled from the zinc negative electrode of example 5 and the zinc negative electrode of comparative example 1, respectively;
fig. 4 is an optical, photomicrograph and scanning electron micrograph of a symmetrical zinc/zinc cell 100h cycle zinc negative electrode obtained from the zinc negative electrode in example 5 and the zinc negative electrode assembly of comparative example 1, respectively;
fig. 5 is a comparison of cycle performance of zinc-iodine full cells assembled from zinc negative electrode materials of example 8 and comparative example 2.
Fig. 6 is a comparison of cycle performance of zinc-iodine full cells assembled from zinc negative electrode materials of example 8 and comparative example 3.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Weighing 0.360g of natural zeolite with the average particle size of 10 mu m and 0.040g of a binder polyvinylidene fluoride (PVDF), mixing the natural zeolite and the PVDF uniformly in a mortar, pouring the mixture into a weighing bottle, adding 1.6mL of N-methylpyrrolidone (NMP) solvent, magnetically stirring for 4 hours at room temperature, after the slurry is uniformly stirred, selecting a four-side preparation device with the thickness of 50-200 mu m, and uniformly scraping and coating the surface of a zinc foil cleaned in advance to form a coating with the thickness of 100 mu m; drying at 60 deg.C for 12 hr.
The dried natural zeolite-coated zinc foil is cut into wafers with phi of 16mm, and then the symmetric batteries are assembled to test relevant electrochemical performances. The electrolyte adopts 1M ZnSO4The solution and the membrane adopt glass fiber.
Example 2
Weighing 0.320g of natural zeolite with the average particle size of 10 mu m and 0.080g of a binder polyvinylidene fluoride (PVDF), mixing the natural zeolite and the PVDF in a mortar, uniformly mixing the natural zeolite and the PVDF in the mortar, pouring the mixture into a weighing bottle, adding 1.6mL of N-methyl pyrrolidone (NMP) solvent, magnetically stirring for 4 hours at room temperature, after uniformly stirring the slurry, selecting a four-side preparation device with the thickness of 50-200 mu m, uniformly scraping and coating the surface of a zinc foil which is cleaned in advance, wherein the thickness of the coating is 100 mu m; drying at 60 deg.C for 12 hr.
The dried natural zeolite-coated zinc foil is cut into 16mm round pieces, and then the symmetrical cell is assembled to test relevant electrochemical performances. The electrolyte adopts 1M ZnSO4The solution and the membrane adopt glass fiber.
Example 3
Weighing 0.280g of natural zeolite with the average particle size of 10 microns and 0.120g of polyvinylidene fluoride (PVDF) binder, mixing the natural zeolite with the PVDF binder, uniformly mixing the natural zeolite and the PVDF binder in a mortar, pouring the mixture into a weighing bottle, adding 1.6mL of N-methylpyrrolidone (NMP) solvent, magnetically stirring for 4 hours at room temperature, selecting a four-side preparation device with the thickness of 50-200 microns after uniformly stirring the slurry, uniformly scraping the surface of a zinc foil cleaned in advance to form a coating with the thickness of 100 microns; drying at 60 deg.C for 12 hr.
The dried natural zeolite-coated zinc foil is cut into 16mm round pieces, and then the symmetrical cell is assembled to test relevant electrochemical performances. The electrolyte adopts 1M ZnSO4The solution and the membrane adopt glass fiber.
Example 4
Weighing 0.320g of nano natural zeolite with the average particle size less than 100nm and 0.080g of a binder polyvinylidene fluoride (PVDF), mixing the materials, uniformly mixing the materials in a mortar, pouring the mixture into a weighing bottle, adding 1.6mL of N-methylpyrrolidone (NMP) solvent, magnetically stirring the mixture for 4 hours at room temperature, after the slurry is uniformly stirred, selecting a four-side preparation device with the thickness of 50-200 mu m, uniformly scraping and coating the surface of a zinc foil which is cleaned in advance, wherein the thickness of the coating is 100 mu m; drying at 60 deg.C for 12 hr.
The dried natural zeolite-coated zinc foil is cut into 16mm round pieces, and then the symmetrical cell is assembled to test relevant electrochemical performances. The electrolyte adopts 1M ZnSO4The solution and the membrane adopt glass fiber.
Example 5
Weighing 0.320g of artificial zeolite with the particle size of 10-100 mu m and 0.080g of polyvinylidene fluoride (PVDF) binder, mixing the artificial zeolite and the PVDF binder uniformly in a mortar, pouring the mixture into a weighing bottle, adding 1.6mL of N-methyl pyrrolidone (NMP) solvent, magnetically stirring for 4 hours at room temperature, after uniformly stirring the slurry, selecting a four-side preparation device with the thickness of 50-200 mu m, and uniformly scraping the surface of a zinc foil cleaned in advance to form a coating with the thickness of 100 mu m; drying at 60 deg.C for 12 hr.
The dried natural zeolite-coated zinc foil is cut into wafers with phi of 16mm, and then the symmetric batteries are assembled to test relevant electrochemical performances. The electrolyte adopts 1M ZnSO4The solution and the membrane adopt glass fiber.
Example 6
Weighing 0.320g of nano natural zeolite with the average particle size less than 100nm and 0.080g of binder Polytetrafluoroethylene (PTFE), mixing the natural zeolite and the binder Polytetrafluoroethylene (PTFE), uniformly mixing the natural zeolite and the binder Polytetrafluoroethylene (PTFE) in a mortar, pouring the mixture into a weighing bottle, adding 4mL of absolute ethyl alcohol solvent, magnetically stirring the mixture at room temperature for 4 hours, after uniformly stirring the slurry, selecting a four-side preparation device with the thickness of 50-200 mu m, and uniformly scraping and coating the surface of a zinc foil cleaned in advance to form a coating with the thickness of 100 mu m; drying at 60 deg.C for 12 hr.
The dried natural zeolite-coated zinc foil is cut into 16mm round pieces, and then the symmetrical cell is assembled to test relevant electrochemical performances. The electrolyte adopts 1M ZnSO4The solution and the membrane adopt glass fiber.
Example 7 preparation I2@ AC composite positive electrode material
Weighing 0.5g I2And 0.5g of activated carbon were thoroughly mixed by grinding. The mixed powder was sealed in a hydrothermal kettle and heated at 90 ℃ for 4 h. During the heating process, I2The mixture is thermally sublimated and injected into the pores of the activated carbon.
Example 8 preparation of Zeolite-Zn I2Zinc-iodine full cell
Will I2@ AC composite positive electrode material, acetylene black and PVDF are uniformly mixed according to the mass ratio (7:2:1), coated on a carbon paper current collector, dried, cut into a wafer with phi of 16mm, zinc foil (Zeolite-Zn) coated by the Zeolite-based ion exchange coating obtained in example 2 is used as a negative electrode, I2The @ AC composite material is a positive electrode, the glass fiber is a diaphragm, and 1M ZnSO4The solution is electrolyte, and a CR2025 button cell is assembled for electrochemical performance test.
Example 9 preparation of MMT-Zn composite negative electrode Material
Weighing 0.320g of natural montmorillonite with the average particle size of 10 mu m and 0.080g of polyvinylidene fluoride (PVDF) binder, mixing the materials, uniformly mixing the materials in a mortar, pouring the mixture into a weighing bottle, adding 1.6mL of N-methylpyrrolidone (NMP) solvent, magnetically stirring for 4 hours at room temperature, after uniformly stirring the slurry, selecting a four-side preparation device with the thickness of 50-200 mu m, uniformly scraping the surface of a zinc foil cleaned in advance, and coating the surface of the zinc foil with the thickness of 100 mu m; drying at 60 deg.C for 12 hr.
Cutting the dried nano natural montmorillonite-coated zinc foil into a wafer with phi of 16mm, and assembling the symmetrical battery to test the relevant electrochemical performance. The electrolyte adopts 1M ZnSO4The solution and the membrane adopt glass fiber.
Comparative example 1
And cutting the zinc foil cleaned in advance into a wafer with phi of 16mm, and assembling the symmetrical battery to test the related electrochemical performance. The electrolyte adopts 1M ZnSO4The solution and the membrane adopt glass fiber.
Comparative example 2
Will I2Mixing the @ AC composite positive electrode material, acetylene black and PVDF uniformly according to a mass ratio (7:2:1), coating the mixture on a carbon paper current collector, drying, cutting a wafer with phi of 16mm, taking pure zinc foil (Zn) as a negative electrode, and I2The @ AC composite material is a positive electrode, the glass fiber is a diaphragm, and 1M ZnSO4The solution is electrolyte, and a CR2025 button cell is assembled for electrochemical performance test.
Comparative example 2 differs from example 8 in that it replaces the zinc negative electrode with a pure zinc foil.
Comparative example 3
Will I2@ AC composite positive electrode material, acetylene black and PVDF are uniformly mixed according to the mass ratio of (7:2:1), coated on a carbon paper current collector, dried, cut into a wafer with phi of 16mm, the nano-montmorillonite coated zinc foil (MMT-Zn) obtained in example 9 is used as a negative electrode, and I is2The @ AC composite material is a positive electrodeGlass fiber as diaphragm, 1M ZnSO4And (4) taking the solution as electrolyte, assembling a CR2025 button cell, and carrying out electrochemical performance test.
The zinc negative electrode in comparative example 1 and the zinc negative electrode in example 5 were tested for I after immersion by an ultraviolet-visible spectrophotometer3 -Solution (0.5mM KI +0.5mM I)2) Ultraviolet and visible absorption spectrum of (1).
The test results are shown in FIG. 1. Comparative example 1 soaked I3 -Ultraviolet-visible absorption spectrum of the solution shows I3 -Has been completely consumed, whereas in example 5 the solution still has I3 -. The results show that this patent can hinder I3 -Contacting the surface of the zinc cathode.
The zinc-iodine full cell assembled in the comparative example 2 and the example 8 was subjected to constant current charging and discharging by a blue cell test system and was left to stand, with a charging voltage of 0.5V to 1.6V and a current density of 2A g-1And standing for 5-50 h. And obtaining a capacity-voltage curve thereof.
The obtained capacity-voltage curve is shown in fig. 2. Comparative example 2 the assembled zinc-iodine full cell lost 12.2% and 49.1% of capacity after standing for 10 hours and 50 hours. Whereas the assembled zinc-iodine cell of example 8 lost only 17.0% of its capacity after standing for 50 h. The result shows that the zinc-iodine full cell can inhibit self-discharge of the zinc-iodine full cell.
The zinc cathode in example 5 and the symmetrical zinc/zinc battery assembled by the zinc cathode in comparative example 1 were tested by a blue cell test system and were subjected to constant current charging and discharging under the test condition of 2.5mA cm-2Current density of 2.5mAh cm-2And obtaining a time-voltage curve thereof.
The obtained cycle stability comparison curve is shown in fig. 3. The symmetrical cell assembled in comparative example 1 fails after 64h of cycling, while the symmetrical cell assembled in example 5 can stably cycle for more than 460h, greatly improving the cycle life of the zinc cathode. Optical, photomicrograph and scanning electron micrograph of the zinc negative electrode after 100h cycling of the symmetrical zinc/zinc cell obtained by assembling the zinc negative electrode of example 5 and the zinc negative electrode of comparative example 1 are shown in fig. 4. In fig. 4, an optical photograph, a photomicrograph, and a scanning electron micrograph are shown from left to right, and the first line is comparative example 1 and the second line is example 5. The zinc negative electrode of comparative example 1 was subjected to perforation, breakage, etc. after cycling, and the dendrite growth thickness was 12 μm. The zinc negative electrode of example 5 was still intact after cycling and the dendrite growth thickness was only 3 μm. The result shows that the zinc cathode dendritic crystal growth can be inhibited, and the zinc cathode deposition is uniform.
Test 4
The zinc-iodine full batteries assembled in the comparative examples 2 and 8 were subjected to constant-current charging and discharging and allowed to stand by a blue battery test system, the charging voltage was 0.5V to 1.6V, and the current density was 2A g-1. And obtaining the cycle performance curve thereof.
The test results are shown in FIG. 5. The capacity retention rate of the zinc-iodine full cell assembled in comparative example 2 was only 25.4% after 125 cycles, while the capacity retention rate of the zinc-iodine full cell in example 8 was still 91.9% after 5600 cycles. The test result shows that the cycle performance and the service life of the zinc-iodine battery can be greatly improved.
Test 5
The zinc-iodine full cell assembled in comparative example 3 and example 8 was subjected to constant current charging and discharging and left standing by a blue cell test system, the charging voltage was 0.5V to 1.6V, and the current density was 2A g-1. And obtaining the cycle performance curve thereof.
The test results are shown in FIG. 6. The capacity retention of the assembled zinc-iodine full cell of comparative example 3 was only 22.1% after 2251 cycles, while the capacity retention of the zinc-iodine full cell of example 8 was still 91.9% after 5600 cycles. The test result shows that compared with a zinc cathode protective coating based on montmorillonite, the zinc-iodine battery can improve the cycle performance and the service life of the zinc-iodine battery to a greater extent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. A zeolite-based ion exchange coating for a long life zinc-iodine battery comprising a zeolite material and a binder, said zeolite material having an average particle size of no more than 100 μm;
when the zeolite-based ion exchange coating is applied to a zinc-iodine battery, the zeolite-based ion exchange coating is attached to the surface of a zinc cathode or a battery diaphragm.
2. A zeolite-based ion exchange coating according to claim 1, having a thickness of 0.02 to 500 μm.
3. A zeolite-based ion exchange coating according to claim 1, wherein said zeolite material is natural zeolite and/or artificial zeolite.
4. The zeolite-based ion exchange coating of claim 1, wherein the binder is one or more of polytetrafluoroethylene, polystyrene, polymethyl methacrylate, polyvinylpyrrolidone, polyacrylonitrile, carboxymethyl cellulose, styrene-butadiene rubber, polyvinylidene fluoride, sodium alginate, polyacrylic acid, polyurethane, polyvinyl alcohol, polyolefins, and fluorinated rubber.
5. A zeolite-based ion exchange coating according to claim 1 wherein the zeolite material is present in the zeolite-based ion exchange coating in an amount of greater than 60 wt%.
6. A zeolite-based ion exchange coating according to claim 1, having an average particle size of not more than 15 μm.
7. A zeolite-based ion exchange coating according to claim 1, having an average particle size of not more than 200 nm.
8. A zeolite-based ion exchange coating according to claim 1, prepared by a process comprising: mixing a zeolite material with a binder to obtain a coating raw material; and coating the coating raw material on the surface of a zinc cathode or a battery diaphragm.
9. A long life zinc-iodine battery comprising a zeolite based ion exchange coating as claimed in any one of claims 1 to 8.
10. The long life zinc-iodine cell of claim 9 comprising a zinc negative electrode or separator material coated with said zeolite based ion exchange coating.
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| CN115312685A (en) * | 2022-08-29 | 2022-11-08 | 郑州大学 | Protective layer of metal zinc cathode of water system zinc ion battery and preparation method of metal zinc cathode |
| CN116169434A (en) * | 2023-04-23 | 2023-05-26 | 宁德新能源科技有限公司 | Separator, electrochemical device and electronic device |
| CN116779829A (en) * | 2023-08-16 | 2023-09-19 | 中石油深圳新能源研究院有限公司 | Organic dual-function composite positive electrode material and preparation method and application thereof |
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| CN112805853A (en) * | 2018-08-14 | 2021-05-14 | 赛伦能源公司 | Protected metallic zinc electrode and method for rechargeable zinc cells and batteries |
| CN112885982A (en) * | 2021-01-11 | 2021-06-01 | 常州工学院 | Nafion/Zn-LSX zeolite composite coating and preparation method and application thereof |
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| CN106450512A (en) * | 2016-09-29 | 2017-02-22 | 清华大学 | Metal battery with molecular sieve solid electrolyte layer |
| CN107666015A (en) * | 2017-09-04 | 2018-02-06 | 天津理工大学 | A kind of aqueous phase electrolyte system zinc iodine secondary cell and preparation method thereof |
| CN112805853A (en) * | 2018-08-14 | 2021-05-14 | 赛伦能源公司 | Protected metallic zinc electrode and method for rechargeable zinc cells and batteries |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115312685A (en) * | 2022-08-29 | 2022-11-08 | 郑州大学 | Protective layer of metal zinc cathode of water system zinc ion battery and preparation method of metal zinc cathode |
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| CN116169434B (en) * | 2023-04-23 | 2023-12-22 | 宁德新能源科技有限公司 | Separator, electrochemical device and electronic device |
| CN116779829A (en) * | 2023-08-16 | 2023-09-19 | 中石油深圳新能源研究院有限公司 | Organic dual-function composite positive electrode material and preparation method and application thereof |
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