CN112072105A - Coating for electrode and preparation method and application thereof - Google Patents
Coating for electrode and preparation method and application thereof Download PDFInfo
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- CN112072105A CN112072105A CN202010856035.0A CN202010856035A CN112072105A CN 112072105 A CN112072105 A CN 112072105A CN 202010856035 A CN202010856035 A CN 202010856035A CN 112072105 A CN112072105 A CN 112072105A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- 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
A coating for an electrode, a preparation method and application thereof. The coating formed by the coating uses cheap nano dielectric filler to adjust the uniformity of zinc deposition, on one hand, the nano channel formed by nano particles can adjust the transmission of zinc ions, on the other hand, the nucleation sites of zinc on an electrode can be increased, and the zinc deposition without dendrites is realized. Meanwhile, the dipole generated by the coating containing the high-dielectric-constant nano filler and the physical barrier effect can effectively isolate water molecules in the electrolyte so as to inhibit corrosion and hydrogen evolution reaction on the zinc cathode, and the stability of the zinc cathode can be obviously improved. The coating formed by the coating has large dielectric filler proportion, can utilize dipole effect generated by the dielectric filler, can adjust the distribution of zinc ions relative to the surface of the electrode through the electrostatic action of the dipoles and the zinc ions, weakens the enhancement effect of a tip electric field, increases nucleation sites on the surface of the electrode, and effectively inhibits the generation of dendritic crystals.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a coating for an electrode, and a preparation method and application thereof.
Background
Energy storage materials are key to clean energy from generation to storage and efficient use. Lithium ion batteries and lead acid batteries, as representatives of high energy density and low cost, respectively, have taken a critical position in the battery industry. However, the price of the lithium ion battery, the storage capacity of lithium resources and the safety of the battery restrict the development of the battery, and the low energy density and environmental pollution of the lead-acid storage battery are not favorable for the sustainable development of the lead-acid storage battery, so that the development of a battery energy storage device with environmental protection, safety and high energy density is very important.
The water system zinc ion battery has the advantages of safety and environmental protection, and the zinc ion battery taking zinc metal as a negative electrode takes the low electrode potential (-0.76V vs. SHE) and the high theoretical capacity (820 mAh g) of zinc -1 ) So that the energy density of the device also has great advantages. However, zinc cathodes can generate dendrites during cycling, causing internal shorting of the cell, and thus cell failure. In addition, the zinc has serious self-corrosion and hydrogen evolution reaction in the electrolyte, and the practical application of the zinc cathode is not facilitated.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a coating for an electrode.
The invention also provides a preparation method of the coating, and an electrode and a current collector with the coating.
The invention provides a coating for an electrode, which comprises the following components in percentage by mass:
dielectric filler: 70 to 98 percent of the total weight of the mixture,
the particle size of the filler is as follows: 1nm to 1 mu m of the total grain size,
adhesive: 2 to 30 percent of the total weight of the mixture,
the relative dielectric constant of the nano dielectric filler is more than or equal to 3000.
In the coating for the electrode, the nano dielectric filler is taken as a core, the relative dielectric constant of the dielectric filler is more than or equal to 3000, a nano channel formed by the coating can adjust a transmission path of zinc ions, can generate obvious space charge polarization, and can generate larger dipole moment under the action of an electric field. The presence of the dipole moment also affects the contact of water molecules with the electrode surface, thus inhibiting corrosion and hydrogen evolution reactions at the electrode.
The binder functions to facilitate adhesion of the coating to other materials, such as electrode surfaces.
The coating for the electrode provided by the invention at least has the following beneficial effects:
the coating formed by the coating uses cheap nano dielectric filler to adjust the uniformity of zinc deposition, increases the nucleation sites of zinc on the electrode and realizes dendrite-free zinc deposition. Meanwhile, the dipole generated by the coating containing the high dielectric constant filler and the physical barrier effect can effectively isolate water molecules in the electrolyte so as to inhibit corrosion and hydrogen evolution reaction on the zinc cathode, and the stability of the zinc cathode can be obviously improved. The coating formed by the coating has large dielectric filler proportion, can utilize dipole effect generated by the dielectric filler, can adjust the distribution of zinc ions relative to the surface of the electrode through the electrostatic action of the dipoles and the zinc ions, weakens the enhancement effect of a tip electric field, increases nucleation sites on the surface of the electrode, and effectively inhibits the generation of dendritic crystals.
The coating formed by the coating can effectively reduce the direct contact between the electrolyte and zinc metal, and prevent the corrosion of zinc and the electrochemical hydrogen evolution reaction, thereby remarkably improving the cycling stability of the zinc cathode. The symmetric battery assembled by Zn @ BT shows that the current density is 0.2mA cm -2 -1mAh cm -2 Under the test condition, the zinc cathode can stably cycle for more than 500 hours, and the cycle life of the zinc cathode is prolonged by more than 8 times compared with that of common zinc foil. Half-cell tests assembled with Zn | | Cu @ BT showed that at 2mA cm -2 -1mAh cm -2 The coulombic efficiency of the current collector dissolution-deposition zinc still remained 99.8% after 440 cycles, and the coating could be stably present on the current collector.
The coating for the electrode provided by the invention is low in cost, is expected to be applied to large-scale industrial production, and has considerable application prospect.
The electrode coating provided by the invention can develop a cheap and efficient modification method of a zinc negative electrode, inhibit the generation and corrosion of zinc dendrites and the generation of hydrogen evolution reaction, and promote the industrialization of a water-based zinc ion battery.
According to one embodiment of the invention, the nano-dielectric filler is selected from BaTiO 3 、CaTiO 3 、Pb(Zr，Ti)O 3 、BaSrTiO 3 、Ba(Zr 0.3 Ti 0.7 )O 3 、Bi 4 Ti 3 O 12 And SrTiO 3 At least one of (a).
According to one embodiment of the present invention, the dielectric filler has a particle size of 1nm to 1 μm.
According to one embodiment of the invention, the binder is a water-insoluble binder.
According to one embodiment of the invention, the binder comprises at least one of polyamide, polyimide, polyurethane, polyvinylidene fluoride, and polytetrafluoroethylene.
The second aspect of the present invention provides a method for preparing the above-mentioned coating for an electrode, which comprises: and dissolving the binder in a solvent, adding the nano dielectric filler, and uniformly dispersing to obtain the coating for the electrode.
The third aspect of the present invention provides an electrode having on its surface a coating layer formed of the paint for an electrode as set forth in any one of claims 1 to 4.
According to one embodiment of the invention, the thickness of the coating is between 1 μm and 300 μm.
According to one embodiment of the present invention, the dielectric filler has a particle size of 1nm to 1 μm, which is the most effective range.
The thickness of the coating can be adjusted according to the process conditions, and the basic principle is that the thickness and the compactness of the coating cannot obviously reduce the transmission speed of ions such as zinc ions.
According to one embodiment of the invention, the electrode is an aqueous ion battery electrode.
According to an embodiment of the present invention, the aqueous ion battery is a zinc ion battery.
The fourth aspect of the present invention provides a current collector having a surface provided with a coating layer formed of the above-described coating material for an electrode.
The coating can be used on common conductive current collectors, such as steel foils, titanium foils, copper foils and tin foils, after the modified current collector is prepared, a certain amount of zinc is deposited through simple electroplating, and the modified current collector can be used as a zinc cathode.
The prepared current collector is used as a zinc cathode, and is more beneficial to industrialization compared with the method of directly coating the coating on a metal foil such as a zinc foil.
The coating is used on a copper current collector to obtain a modified current collector with ultra-long cycle life and ultra-high coulombic efficiency, and the modified current collector or the zinc negative electrode can be industrially produced on a large scale.
Drawings
FIG. 1 shows the cell density at 0.2mA cm for the symmetrical cells of comparative example 1 and example 2 of the present invention -2 -1mAh cm -2 And (4) testing the charging and discharging result under the condition.
FIG. 2 shows the cell density at 0.5mA cm for the symmetrical cells of comparative example 1 and example 2 of the present invention -2 -0.5mAh cm -2 And (4) testing results of charging and discharging under the conditions.
FIG. 3 shows the cell density at 0.2mA cm for the symmetrical cells of comparative example 1 and example 2 of the present invention -2 -1mAh cm -2 Voltage hysteresis graph of (2).
FIG. 4 shows the cells of comparative example 2 and example 3 of the present invention at 0.5mA cm -2 -0.5mAh cm -2 And (4) testing the charging and discharging result under the condition.
FIG. 5 shows a comparative example of the present invention2 and the cell in example 3 at 2mA cm -2 -1mAh cm -2 And (4) testing results of charging and discharging under the conditions.
Figure 6 is a plot of nucleation overpotential versus voltage hysteresis for the half cells of comparative example 2 and example 3 of the present invention.
Fig. 7 is a graph of the capacity voltage of the full zinc-manganese battery according to comparative example 3 and example 2 of the present invention.
FIG. 8 is a 1000-fold magnification representation of the electrode surface micro-topography of example 1 of the present invention.
FIG. 9 is a 10000 times magnification of the electrode surface micro-topography of example 1 of the present invention.
FIG. 10 is a surface micro-topography of a zinc foil of example 1 of the present invention.
Fig. 11 is a schematic diagram showing the XRD detection results of the electrode surface coating of example 1 of the present invention.
Fig. 12 is a schematic of the micro-topography of zinc on bare copper foil of example 3 of the present invention.
Fig. 13 is a schematic of the microstructure of zinc on BT coated copper foil according to example 3 of the present invention.
Fig. 14 is a graph showing the results of the battery performance test in example 4 of the present invention.
Fig. 15 is a graph showing the results of the battery performance test in example 5 of the present invention.
Fig. 16 is a graph showing the results of the battery performance test in example 6 of the present invention.
Fig. 17 is a graph showing the results of the battery performance test in example 7 of the present invention.
Detailed Description
The invention aims to solve the dendritic crystal problem of a zinc cathode of a water system zinc ion battery, and provides an efficient solution for corrosion and hydrogen evolution reaction, the effectiveness of the coating is illustrated by combining with the attached drawings, the illustration is only to illustrate that the piezoelectric or ferroelectric nano filler with high dielectric constant is designed to inhibit dendritic crystal, and simultaneously can solve the corrosion and hydrogen evolution reaction, so that the selection of the preparation methods of the solvent, the binder and the coating is as normal as possible, and is only to simplify the operation process, but the process does not limit the development of the invention on related methods.
Comparative example 1
Cutting 20 μm thick zinc foil into 1cm 2 2mol L of the round electrode plate -1 ZnSO 4 +0.1mol L -1 MnSO 4 The solution of (1) was used as an electrolyte, commercial glass fiber was used as a separator, a Zn | Zn symmetrical battery was assembled with a button battery case of 2025, and charge and discharge tests were performed under 0.2mA cm and 0.2mA cm respectively -2 (Current Density of deposition) -1mAh cm -2 (area capacity of deposition), and 0.5mA cm -2 -0.5mAh cm -2 And analyzing the polarization of the material in the charging and discharging process. As shown in FIGS. 1 to 3, the comparative Zn-Zn symmetric batteries had cycle lives of 75 hours (0.2 mA cm) -2 -1mAh cm -2 ) And 28h (0.5 mA cm) -2 -0.5mAh cm -2 ) The polarization voltage test result shows that the Zn symmetrical battery has large polarization voltage in the dissolving and depositing process of zinc.
Comparative example 2
Cutting 20 μm copper foil and 20 μm zinc foil into 1cm 2 The electrolyte, separator and battery case of comparative example 1 were used for the wafer electrode of (1). Assembling a Zn & ltI & gt Cu half cell, wherein Cu is used as a positive electrode, zn is used as a negative electrode, and the concentration of the Zn is 0.5mA cm -2 -0.5mAh cm -2 Is discharged under the conditions of (1), and then is discharged at a constant current of 0.5mA cm -2 The method comprises the steps of charging, wherein the charging cut-off voltage is 1V, and the representation of the coulomb efficiency and the cycle stability of the Cu current collector is obtained through testing. The Zn | | Cu half-cell test results show that at 0.5mA cm, as shown in FIGS. 4 to 6 -2 -0.5mAh cm -2 The half cell was stable for 230 cycles under the test conditions of (1), the first nucleation overpotential of zinc on Cu was 54mV. At 2mA cm -2 -1mAh cm -2 Can be stably cycled for 440 times under the test conditions.
Comparative example 3
Cutting zinc foil into 1cm 2 The wafer electrode of (1) was used as a negative electrode of an aqueous zinc-manganese battery using the electrolyte, separator and battery can of comparative example 1, and then commercial MnO was used 2 The powder material is used as a positive electrode material and a positive electrodeThe preparation process of the pole piece comprises the step of preparing commercialized MnO 2 PVDF and acetylene black are uniformly ground and stirred into uniform slurry according to the proportion of 7.5 2 After the positive pole piece is assembled into a full cell, the charging and discharging test is carried out after the full cell is placed for 6 hours. The parameters of the charge and discharge test are as follows: charging to 1.9V with constant current, discharging to 0.8V cut-off voltage with constant current, and charging and discharging current density of 200mA g -1 And obtaining the cycle performance parameters of the full battery. As shown in FIG. 7, comparative example Zn. DELTA.MnO 2 The specific discharge capacity of the tenth circle is 258mAh g -1 The discharge plateau is around 1.3V.
Example 1
PVDF is dissolved in nitrogen-nitrogen dimethyl pyrrolidone solution, and then 100nm BaTiO is added 3 Adding the nano particles into the uniform solution, and performing ultrasonic dispersion and magnetic stirring to obtain uniform slurry, wherein the mass ratio of PVDF: baTiO 2 3 Is 5. Cleaning and polishing zinc foil as substrate, uniformly coating the slurry on the zinc foil by using a film coating machine, vacuum drying at 60 deg.C for not less than 3 hr, and cutting into pieces of 1cm -2 The wafer electrode is ready for use. As shown in fig. 8, baTiO was coated 3 The zinc foil surface of the coating was covered with a uniform layer of nanoparticles, and further magnified, the coating was found to have uniform pores, as shown in fig. 9, which could act as channels for ion transport. This is a significant difference from bare zinc foil, as shown in figure 10. Characterization of the nano-BT using XRD found that the nanoparticles were a single BT phase, free of any impurities, as shown in figure 11.
Example 2
BaTiO prepared in example 1 was used 3 Zn @ BT symmetric battery assembled by using coated zinc foil as electrode and comparing electrolyte, diaphragm and battery shell used in example 1, and charging and discharging current bars are differentThe cycling stability of the cells was tested at 0.5mA cm -2 -0.5mAh cm -2 The symmetric battery can stably cycle for more than 420 hours under the charging and discharging conditions, which is 22 times that of the comparative example Zn | | Zn symmetric battery, as shown in FIG. 2, and the Zn @ BT negative electrode has lower hysteresis voltage and nucleation overpotential, as shown in FIG. 3. At 0.2mA cm -2 -1mAh cm -2 Can stably circulate for 500 hours under the charging and discharging conditions, is 7 times of that of a Zn (I) Zn symmetrical battery, and is shown in figure 1. Similarly, mnO in comparative example was used 2 Positive electrode assembly full cell tests found that the zn @ bt negative electrode also exhibited better full cell performance, as shown in fig. 7.
Example 3
The slurry of example 1 was uniformly coated on a cleaned copper foil, the thickness of the coating was controlled, and then vacuum-dried at 60 ℃ for not less than 3 hours and cut into 1cm 2 The wafer current collector (Cu @ BT) of (1). Using the electrolyte, the separator and the battery case of comparative example 1, and then using the bare zinc foil as the negative electrode, the half-cell was assembled with Cu @ BT to form a half-cell Zn | | Cu @ BT, which was found by the test to be at 0.5mA cm -2 -0.5mAh cm -2 Can be stably cycled for more than 220 times under the charging and discharging conditions, which is 9 times of that of the Zn & ltI & gt Cu half cell of the comparison example, as shown in figure 4. Meanwhile, the study on the deposition voltage of zinc on the current collector for the first time shows that the Cu @ BT current collector has a lower nucleation overpotential of zinc of 26mV, which is far lower than the nucleation overpotential of a bare copper foil of 54mV, as shown in FIG. 6. Also, at 2mA cm -2 -1mAh cm -2 Under the circulation condition of (1), the Cu @ BT current collector can stably circulate for 440 times, and can still maintain the coulomb efficiency of 99.8 percent, which is obviously superior to the circulation life and the coulomb efficiency of the bare copper foil, as shown in figure 5. Scanning electron microscopy also verified the validity of the above results and observed that zinc was deposited as non-uniform, loose zinc dendrites on bare copper foil, as shown in fig. 12, and as dense, uniform zinc on BT coated copper foil, as shown in fig. 13.
Example 4
PVDF is dissolved in nitrogen-nitrogen dimethyl pyrrolidone solution, and then 300nm of flaky Bi 4 Ti 3 O 12 Adding the mixture into a uniform solution, and performing ultrasonic dispersion and magnetic stirring to obtain uniform slurry, wherein the mass ratio of PVDF: bi 4 Ti 3 O 12 Is 10. Cleaning and polishing zinc foil as substrate, uniformly coating the slurry on the zinc foil by using a film coating machine, vacuum drying at 60 deg.C for not less than 3 hr, and cutting into pieces of 1cm -2 The wafer electrode is ready for use. Then assembling Zn @ Bi 4 Ti 3 O 12 ||Zn@Bi 4 Ti 3 O 12 Symmetrical cells (using the same electrolyte, separator and cell casing as in the comparative example) were at 0.5mA cm -2 -0.5mAh cm -2 The following tests gave symmetric cell performance, as shown in fig. 14, which was stable for over 380h.
Example 5
PVDF was dissolved in N-dimethylpyrrolidone solution, and 1 μm BaSrTiO was added 3 Adding the particles into the uniform solution, and performing ultrasonic dispersion and magnetic stirring to obtain uniform slurry, wherein the mass ratio of PVDF: baSrTiO 3 Is 8. Cleaning and polishing zinc foil as substrate, uniformly coating the slurry on the zinc foil by using a film coating machine, vacuum drying at 60 deg.C for not less than 3 hr, and cutting into pieces of 1cm -2 The wafer electrode is ready for use. Then assembling Zn @ BaSrTiO 3 ||Zn@BaSrTiO 3 Symmetrical cells (using the same electrolyte, separator and cell housing as in the comparative example) at 2mA cm -2 -1mAh cm -2 The following tests gave symmetrical cell performance, as shown in fig. 15, which can be cycled stably for over 180 hours.
Example 6
PVDF was dissolved in a nitrogen-dimethyl pyrrolidone solution, and then 30nm of Pb (Zr, ti) O was added 3 Adding the nano particles into the uniform solution, and performing ultrasonic dispersion and magnetic stirring to obtain uniform slurry, wherein the mass ratio of PVDF: pb (Zr, ti) O 3 Is 6. Cleaning and polishing the copper foilUniformly coating the slurry on a copper foil by using a film coating machine, drying at 60 ℃ in vacuum for not less than 3h, and cutting into pieces of 1cm -2 The wafer electrode is ready for use. Then assembling Cu @ Pb (Zr, ti) O 3 I Zn half-cell (using the same electrolyte, separator and cell casing as in the control) at 2mA cm -2 -1mAh cm -2 The following test results in symmetrical battery performance, as shown in fig. 16, the stable cycle can exceed 360h, and the coulomb efficiency of the battery can still be maintained at 99.7%.
Example 7
PVDF was dissolved in N-dimethylpyrrolidone solution, and 5 μm BaTiO was then added 3 Adding the particles into the uniform solution, and performing ultrasonic dispersion and magnetic stirring to obtain uniform slurry, wherein the mass ratio of PVDF: baTiO 2 3 Is 5. Cleaning and polishing zinc foil as substrate, uniformly coating the slurry on the zinc foil (with the coating thickness of example 1) by using a coating machine, vacuum drying at 60 deg.C for not less than 3 hr, and cutting into pieces of 1cm -2 The wafer electrode is ready for use. Then, a Zn @ BT | | Zn @ BT symmetric cell (using the same electrolyte, separator and cell case as in the comparative example) was assembled at 2mA cm -2 -1mAh cm -2 The following test gave symmetric cell performance, as shown in fig. 17, which was stable for 190h.
As can be seen from the results of the above comparative examples 1 to 3 and examples 1 to 6, a filler having a high dielectric constant such as BaTiO 3 The BT-coated zinc cathode with excellent performance can be prepared by uniformly coating a small amount of adhesive on the surface of a zinc cathode, or the BT-coated zinc cathode is coated on a current collector to prepare a modified current collector with high coulombic efficiency and stable circulation. On one hand, the high-dielectric-constant nano particles can regulate and control the transmission flux of zinc ions relative to the surface of the electrode through strong space charge polarization, and meanwhile, the polarized coating can effectively regulate the ion transmission of the tips of dendritic crystals by forming special dipoles, so that the leveling effect is achieved, the concentrated deposition of zinc on the electrode is avoided, the area capacity of zinc deposition is reduced, and the piercing risk of a diaphragm is reduced; on the other hand, electrostatic effects produced by the dipole of the coatingThe direct contact between the electrolyte and zinc metal is effectively reduced by the force and physical barrier effect, the corrosion and hydrogen evolution reaction of the zinc cathode are inhibited, and the circulation stability of the zinc cathode in water system electrolyte is remarkably improved. Examples 1 and 7 show that the dielectric filler with a particle size of 100nm has better effect than the dielectric filler with a particle size of 5 μm, because the nanochannels formed by the coating can better regulate the uniform transmission of zinc ions.
The nano dielectric filler is BaTiO 3 、CaTiO 3 、Pb(Zr，Ti)O 3 、BaSrTiO 3 、Ba(Zr 0.3 Ti 0.7 )O 3 、Bi 4 Ti 3 O 12 And SrTiO 3 At least one of (a).
The nano dielectric filler has a large dielectric constant, can generate obvious space charge polarization, and can generate a large dipole moment under the action of an electric field. In the deposition process, nano particles form a nano channel to regulate and control the uniform transmission of zinc ions, on the other hand, the coating forms a positive charge layer surrounding the electrode under the action of electric fields at two ends of the electrode, the transmission of the zinc ions is influenced by the electrostatic action generated by dipoles under the action of charges, and at the position with strong electric field at the tip, the charge separation of the dipoles generated by the dielectric material is more obvious, so that the zinc ions are difficult to cross over the dipole ends with positive charges, and the growth of dendrites is not facilitated, thereby achieving the leveling effect.
Claims (9)
1. The coating for the electrode is characterized by comprising the following components in percentage by mass:
dielectric filler: 70 to 98 percent of the total weight of the mixture,
adhesive: 2 to 30 percent of the total weight of the mixture,
the grain diameter of the dielectric filler is 1nm-1 mu m,
the relative dielectric constant of the dielectric filler is more than or equal to 3000.
2. The coating material for an electrode as claimed in claim 1, wherein the dielectric filler is BaTiO 3 、CaTiO 3 、Pb(Zr，Ti)O 3 、BaSrTiO 3 、Ba(Zr 0.3 Ti 0.7 )O 3 、Bi 4 Ti 3 O 12 And SrTiO 3 At least one of (1).
3. The coating material for an electrode as claimed in claim 1 or 2, wherein the binder comprises at least one of polyamide, polyimide, polyurethane, polyvinylidene fluoride and polytetrafluoroethylene.
4. A method for preparing the coating material for an electrode according to any one of claims 1 to 3, characterized in that the method comprises: and dissolving the binder in a solvent, adding the dielectric filler, and uniformly dispersing to obtain the coating for the electrode.
5. An electrode characterized in that the surface of the electrode has a coating layer formed of the paint for electrodes described in any one of claims 1 to 4.
6. The electrode of claim 5, wherein the coating has a thickness of 1 μm to 300 μm.
7. The electrode of claim 5, wherein the electrode is an aqueous ion battery electrode.
8. The electrode according to claim 7, wherein the aqueous ion battery is a zinc ion battery.
9. A current collector characterized in that the surface of the current collector has a coating layer formed of the coating material for electrodes described in any one of claims 1 to 3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112838211A (en) * | 2020-12-30 | 2021-05-25 | 中南大学 | Modification method of zinc metal negative electrode, product and application thereof |
| CN113851646A (en) * | 2021-09-29 | 2021-12-28 | 江南大学 | Zinc ion battery cathode material based on boron nitride film and preparation method thereof |
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| CN113851646A (en) * | 2021-09-29 | 2021-12-28 | 江南大学 | Zinc ion battery cathode material based on boron nitride film and preparation method thereof |
| CN113851646B (en) * | 2021-09-29 | 2023-03-28 | 江南大学 | Zinc ion battery cathode material based on boron nitride film and preparation method thereof |
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