CN114142032A - Zinc ion battery and method for improving zinc negative electrode cycle performance of zinc ion battery - Google Patents

Zinc ion battery and method for improving zinc negative electrode cycle performance of zinc ion battery Download PDF

Info

Publication number
CN114142032A
CN114142032A CN202111183724.0A CN202111183724A CN114142032A CN 114142032 A CN114142032 A CN 114142032A CN 202111183724 A CN202111183724 A CN 202111183724A CN 114142032 A CN114142032 A CN 114142032A
Authority
CN
China
Prior art keywords
zinc
zif
ion battery
composite coating
negative electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111183724.0A
Other languages
Chinese (zh)
Inventor
钱瑶
董梦飞
陈璞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ruihai Bo Changzhou Energy Technology Co ltd
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN202111183724.0A priority Critical patent/CN114142032A/en
Publication of CN114142032A publication Critical patent/CN114142032A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a zinc ion battery and a method for improving the cycle performance of a zinc cathode of the zinc ion battery. In the zinc ion battery, a ZIF-8 composite coating is arranged on the surface of a Zn cathode and/or on one side of a diaphragm close to the Zn cathode, and the composite coating comprises ZIF-8 and a binder. The zinc ion battery utilizes the ZIF-8 composite coating to effectively inhibit the growth of zinc dendrite and the occurrence of side reactions, can obviously improve the cycling stability of a zinc cathode and the coulomb efficiency of stripping/deposition under larger surface capacity, and has better electrochemical performance and longer service life.

Description

Zinc ion battery and method for improving zinc negative electrode cycle performance of zinc ion battery
Technical Field
The invention belongs to the field of batteries, and particularly relates to a zinc ion battery and a method for improving the cycle performance of a zinc cathode of the zinc ion battery.
Background
In a zinc ion aqueous battery, the stability and life of the aqueous zinc ion battery are severely restricted by problems such as severe dendrite growth due to non-uniform dissolution and deposition of Zn, and gassing and self-corrosion due to a side reaction between zinc and water. The current research on negative electrodes is mostly based on the use of electrolyte additives and the construction of artificial SEI coatings, but these studies are based onThe surface capacity of the powder is mostly less than 1mAh/cm2And the requirement of practical application is far from being met.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose a zinc ion battery and a method of improving the cycling performance of a zinc negative electrode of a zinc ion battery. The zinc ion battery utilizes the ZIF-8 composite coating to effectively inhibit the growth of zinc dendrite and the occurrence of side reactions, can obviously improve the cycling stability of a zinc cathode and the coulomb efficiency of stripping/deposition under larger surface capacity, and has better electrochemical performance and longer service life.
The present application is primarily based on the following problems and findings:
zinc metal cathodes have the following major drawbacks in aqueous battery applications: 1. the dendrite phenomenon is serious in the charging and discharging process, so that the service life of the battery is limited; 2. the side reaction of the electrolyte and the aqueous solution is more, and the gassing phenomenon exists, so that the battery system is unstable. The inventor finds that the ZIF-8 not only has hydrophobic and oleophilic properties, but also has ion exchange capacity, and the inventor assumes that the ZIF-8 can be used for forming a coating on one side of a zinc metal negative electrode or a diaphragm close to the zinc negative electrode, so as to inhibit the problems of gassing, self-corrosion and the like caused by side reaction between zinc and water in a zinc ion water system battery, and simultaneously inhibit the growth of zinc dendrites, thereby achieving the purpose of prolonging the cycle life of the zinc negative electrode.
To this end, according to a first aspect of the invention, a zinc-ion battery is proposed. According to the embodiment of the invention, the surface of the Zn negative electrode and/or one side of the diaphragm close to the Zn negative electrode are/is provided with the ZIF-8 composite coating, and the composite coating comprises ZIF-8 and a binder. Compared with the prior art, the zinc ion battery at least has the following advantages: 1. the high hydrophobicity, the high stability and the Zn ion exchange capacity of the ZIF-8 composite coating can be utilized to block the gassing reaction between the zinc cathode and water and the self-corrosion phenomenon of the zinc cathode, inhibit the growth of zinc dendrites to cause the internal micro short circuit of the battery, and ensure the conductivity of the zinc ion battery; 2. can be used under larger surface capacity (for example)E.g. 4mAh/cm2) The method improves the coulombic efficiency of Zn dissolution and deposition while inhibiting dendritic crystal growth and prolonging the cycle life, and inhibits hydrogen evolution reaction. In conclusion, the zinc ion battery has better electrochemical performance and longer service life.
In addition, the zinc-ion battery according to the above embodiment of the invention may also have the following additional technical features:
in some embodiments of the invention, the binder is PVDF.
In some embodiments of the present invention, the mass ratio of the ZIF-8 to the PVDF is (4-12): 1.
in some embodiments of the present invention, the thickness of the ZIF-8 composite coating is 5 to 50 μm.
In some embodiments of the present invention, the ZIF-8 composite coating is formed using a spin coating process or a blade coating process,
in some embodiments of the present invention, the spin coating speed is 1000-8000 rpm, and the spin coating time is 10-60 s.
In some embodiments of the present invention, the ZIF-8 is prepared by the following steps: mixing and reacting a zinc ion solution and a 2-methylimidazole solution; the reaction solution was subjected to centrifugal drying to obtain ZIF-8 particles.
In some embodiments of the invention, the molar ratio of the zinc ions to the 2-methylimidazole is 1: (1-3).
In some embodiments of the invention, the solute of the zinc ion solution comprises at least one selected from the group consisting of zinc sulfate, zinc nitrate, and zinc acetate.
In some embodiments of the invention, the zinc-ion battery is an aqueous battery.
Based on the same inventive concept, according to a second aspect of the invention, the invention provides a method for improving the cycle performance of a zinc negative electrode of a zinc ion battery. According to an embodiment of the invention, the method comprises: and forming a ZIF-8 composite coating on the surface of the Zn negative electrode and/or on one side of the separator close to the Zn negative electrode, wherein the composite coating comprises ZIF-8 and a binder. Compared with the prior art, the method has simple process and can also be used forCan effectively inhibit the growth of zinc dendrites and the occurrence of side reactions, and can realize a large surface capacity (such as 4 mAh/cm)2) The cycling stability of the zinc cathode and the coulomb efficiency of stripping/deposition are obviously improved, so that the zinc ion battery has good electrochemical performance and long service life, and has extremely high application value in a zinc ion water system battery.
In some embodiments of the invention, the binder is PVDF.
In some embodiments of the present invention, the mass ratio of the ZIF-8 to the PVDF is (4-12): 1.
in some embodiments of the present invention, the thickness of the ZIF-8 composite coating is 5 to 50 μm.
In some embodiments of the invention, the ZIF-8 composite coating is formed by a spin-coating method or a blade coating method, and the blade coating thickness is 5-50 μm; the spin coating speed is 1000-8000 rpm, and the spin coating time is 10-60 s.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a graph of cell voltage as a function of time assembled according to comparative example 1 of the present invention;
FIG. 2 is an SEM image of zinc negative electrode ZIF-8-PVDF-TB @ Zn prepared according to example 1 of the present invention at different magnifications.
Fig. 3 is a graph of the voltage of a battery assembled according to example 1 of the present invention as a function of time.
Fig. 4 is a graph of the voltage of a battery assembled according to example 2 of the present invention as a function of time.
Fig. 5 is a graph of the voltage of a battery assembled according to example 3 of the present invention as a function of time.
Fig. 6 is a graph of the voltage of a cell assembled according to comparative example 2 of the present invention as a function of time.
Fig. 7 is a graph of the voltage of a cell assembled according to comparative example 3 of the present invention as a function of time.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to a first aspect of the invention, a zinc-ion battery is presented. According to the embodiment of the invention, the surface of the Zn negative electrode and/or the side of the diaphragm close to the Zn negative electrode in the zinc ion battery are/is provided with the ZIF-8 composite coating, the ZIF-8 composite coating comprises ZIF-8 (namely 2-methylimidazolium zinc) and a binder, and preferably, the ZIF-8 composite coating can be formed on the surface of the Zn negative electrode. The inventor finds that the ZIF-8 not only has hydrophobicity and lipophilicity and high stability, but also has ion exchange capacity, and can form a coating on one side of a zinc metal negative electrode or a diaphragm close to the zinc negative electrode by utilizing the ZIF-8 so as to inhibit the problems of gassing, self-corrosion and the like caused by side reaction between zinc and water in a zinc ion water system battery; further, the inventors have also found that by providing a ZIF-8 composite coating, it is also possible to provide a large surface capacity (e.g., 4 mAh/cm)2) The method improves the coulombic efficiency of Zn dissolution and deposition while inhibiting dendritic crystal growth and prolonging the cycle life, and inhibits hydrogen evolution reaction. Therefore, the zinc ion battery has better electrochemical performance and longer service life.
The zinc-ion battery according to the above embodiment of the present invention will be described in detail.
According to some embodiments of the present invention, the type of the binder used in forming the ZIF-8 composite coating is not particularly limited, and those skilled in the art can select the binder according to actual needs, for example, the binder may include common additives such as PVDF, and preferably, the binder may be PVDF, and the inventors have found that PVDF has good mechanical strength, chemical stability, electrochemical stability, and thermal stability, has good affinity to an electrolyte, has low swelling rate in the electrolyte, high binding strength, and certain hydrophobicity, and can be used as the binder to uniformly and stably coat the ZIF-8 material on the surface of the zinc negative electrode or on the side of the separator close to the zinc negative electrode, so that the formed ZIF-8 composite coating can more effectively block the gassing reaction between the zinc negative electrode and water and the self-corrosion phenomenon of the zinc negative electrode, and the problem of micro short circuit in the battery caused by the growth of zinc dendrite is inhibited, so that the aim of inhibiting the growth of the zinc dendrite in the zinc ion battery and prolonging the cycle life of the zinc cathode under larger surface capacity is fulfilled.
According to some embodiments of the present invention, the mass ratio of ZIF-8 to PVDF may be (4-12): 1, for example, 12/1, 11/1, 10/1, 9/1, 8/1, 7/1, 6/1, 5/1, 4/1 or any ratio between 12:1 and 4:1, and the inventor finds that PVDF has certain hydrophobicity but does not have ion conduction performance, and if the relative amount of PVDF is too large, the interface internal resistance is too high, and the battery cannot work normally; if the relative dosage of PVDF is too small, the bonding effect of the ZIF-8 and a zinc cathode or a diaphragm is difficult to ensure, the zinc cathode is separated out, the stability of the ZIF-8 composite coating is reduced, and the cycle performance of the battery is obviously reduced.
According to still other embodiments of the present invention, the thickness of the ZIF-8 composite coating layer may be 5 to 50 μm, for example, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm, and preferably 5 to 20 μm, and the inventors found that if the thickness of the ZIF-8 composite coating layer is too small, the problems of gassing and self-corrosion and zinc dendrite growth due to side reaction between zinc and water in the zinc ion aqueous battery may not be effectively suppressed, and if the thickness of the ZIF-8 composite coating layer is too large, not only the energy density of the battery may be affected, but also raw material waste may be caused, and in the present invention, by controlling the ZIF-8 composite coating layer to the above thickness range, both good hydrophobicity and ion exchange capability may be ensured, and no significant negative effect may be generated on the energy density of the battery, and the comprehensive performance of the battery can be improved.
According to still other embodiments of the present invention, the method for forming the ZIF-8 composite coating layer in the present invention is not particularly limited, and those skilled in the art can select the method according to actual needs, for example, a ZIF-8 composite coating layer slurry is prepared in advance, preferably, PVDF and an organic solvent are mixed to prepare a glue, ZIF-8 and an organic solvent are mixed to form a solution, then, the glue solution and the ZIF-8 solution are mixed to prepare a composite coating layer slurry, and then, the slurry is uniformly coated on the zinc negative electrode and/or the separator by using a spin coating method or a blade coating method, etc. so as to form the ZIF-8 composite coating layer, and the improved zinc negative electrode or the separator is obtained, wherein, the spin coating method is preferably used; in addition, when the blade coating method is adopted, the blade coating thickness can be 5-50 μm, and preferably about 10 μm; further, when the spin coating method is adopted, the rotation speed of the spin coating can be 1000-8000 rpm, such as 2000rpm, 3000 rpm, 4000 rpm, 5000 rpm, 6000rpm and 7000 rpm, and the like, the spin coating time can be 10-60 s, such as 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s or 55s, and the like, and the inventor finds and verifies through a large number of experiments that a more uniform and compact ZIF-8 composite coating can be obtained by selecting the spin coating method and controlling the spin coating conditions, so that the problems of gassing, self-corrosion, zinc dendrite growth and the like caused by side reaction between a zinc negative electrode and water can be more favorably inhibited; for another example, the spin-coating speed is preferably 5500 to 6500 rpm, and the spin-coating time is preferably 25 to 35 seconds.
According to still other embodiments of the present invention, ZIF-8 (i.e., zinc 2-methylimidazolium) can be prepared by the following steps: mixing and reacting a zinc ion solution and a 2-methylimidazole solution in advance, and then centrifugally drying a reaction solution to obtain ZIF-8 particles, wherein the solvents adopted by the zinc ion solution and the 2-methylimidazole solution are not particularly limited, and can be selected by a person skilled in the art according to actual needs as long as the zinc salt and the imidazole salt can be subjected to coordination complex precipitation, and for example, the solvents adopted by the zinc ion solution and the 2-methylimidazole solution can be respectively and independently selected from water and/or organic solvents such as methanol, ethanol and the like; in addition, the solute adopted by the zinc ion solution is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the solute (zinc salt) can be zinc sulfate, zinc nitrate, zinc acetate, and the like, for example, deionized water and zinc sulfate can be preferred.
According to still other embodiments of the present invention, the molar ratio of zinc ions to 2-methylimidazole may be 1: (1-3), for example, the ratio may be any ratio of 1/1, 1/1.2, 1/1.5, 1/2, 1/2.5, or 1/1 to 1/3, preferably about 1/2.5, and the inventors found that the molar ratio of zinc ion concentration is too large or too small, which affects the yield of ZIF-8, and in the present invention, it is more advantageous to improve the utilization rate of the raw material and the yield of ZIF-8.
According to still other specific embodiments of the invention, the zinc ion battery can be an aqueous battery, so that the growth of zinc dendrites and the occurrence of side reactions can be effectively inhibited based on the arrangement of the ZIF-8 composite coating, the cycling stability of a zinc cathode and the coulomb efficiency of stripping/deposition can be improved under a larger surface capacity, and the common inherent defects of the existing zinc ion aqueous battery can be effectively overcome, so that the zinc ion battery has better electrochemical performance and longer service life, and the comprehensive performance and the cost performance of the zinc ion aqueous battery are improved.
In summary, compared with the prior art, the zinc ion battery of the above embodiment of the invention has at least the following advantages: 1. the high hydrophobicity, the high stability and the Zn ion exchange capacity of the ZIF-8 composite coating can be utilized to block the gassing reaction between the zinc cathode and water and the self-corrosion phenomenon of the zinc cathode, inhibit the growth of zinc dendrites to cause the internal micro short circuit of the battery, and ensure the conductivity of the zinc ion battery; 2. can be used under a larger surface capacity (for example, 4 mAh/cm)2) In inhibitingThe dendritic crystal growth improves the circulation stability, improves the coulomb efficiency of Zn dissolution and deposition, and inhibits the hydrogen evolution reaction. In conclusion, the zinc ion battery has better electrochemical performance and longer service life.
Based on the same inventive concept, the invention also provides a method for improving the cycle performance of the zinc negative electrode of the zinc ion battery according to the second aspect of the invention. According to an embodiment of the invention, the method comprises: and forming a ZIF-8 composite coating on the surface of the Zn negative electrode and/or one side of the diaphragm close to the Zn negative electrode, wherein the composite coating comprises ZIF-8 and a binder. Compared with the prior art, the method has simple process, can effectively inhibit the growth of zinc dendrite and the generation of side reaction, and can realize a larger surface capacity (for example, 4 mAh/cm)2) The cycling stability of the zinc cathode and the coulomb efficiency of stripping/deposition are obviously improved, so that the zinc ion battery has good electrochemical performance and long service life, and has extremely high application value in a zinc ion water system battery.
According to an embodiment of the present invention, the binder used in the method may preferably be PVDF; the mass ratio of ZIF-8 to PVDF can be (4-12): 1; the thickness of the composite coating can be 5-50 μm; the composite coating can be formed by adopting a spin coating method or a blade coating method, and the blade coating thickness can be 5-50 mu m; the spin coating speed can be 1000-8000 rpm, and the spin coating time can be 10-60 s. Therefore, the protection effect of the ZIF-8 composite coating on the negative electrode is better improved, the growth of zinc dendrites in the zinc ion battery can be better inhibited, and the cycle life of the zinc negative electrode is prolonged. It should be noted that, the method for improving the zinc negative electrode cycling performance of the zinc ion battery in the present invention is proposed based on the same inventor concept as the above zinc ion battery, and the features and effects described for the above zinc ion battery are also applicable to the method for improving the zinc negative electrode cycling performance of the zinc ion battery, and are not described again.
In summary, the zinc ion battery and the method for improving the cycle performance of the zinc cathode of the zinc ion battery according to the embodiments of the invention have at least the following advantages: 1. ZIF-8 composite coating (preferably ZIF-8-PVDF coating) can be adopted to prevent direct contact between zinc cathode and water and inhibit self-corrosionAnd adverse effects of gassing on the battery, improving coulombic efficiency of Zn dissolution/deposition; 2. after the zinc cathode is modified by the ZIF-8 composite coating (preferably the ZIF-8-PVDF coating), the growth of zinc dendrites of the cathode can be inhibited, the formation of micro short circuit in the battery can be avoided, the cycle stability and the service life of the cathode can be improved, and the cathode can be used even under the condition of larger surface capacity (such as 4 mAh/cm/h)2) The coulomb efficiency of Zn dissolution and deposition can be improved and the hydrogen evolution reaction can be inhibited while the growth of dendritic crystals is inhibited and the cycle life is prolonged; 3. the battery has good cycling stability and long service life.
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Comparative example 1
Assembling the battery: in the experiment, copper foil is used as a positive electrode, Zn foil is used as a negative electrode, and a diaphragm is AGM. The electrolyte is dissolved in water by taking water as a solvent, zinc sulfate as zinc salt and manganese sulfate as manganese salt, and Zn2+Mn at a concentration of 1.8mol/L2+The concentration is 0.2 mol/L. And (3) testing the battery: the capacity of the set surface is 4mAh/cm in the environment of 25 DEG C2The cut-off voltage was 0.5V.
And (3) testing the battery: in an environment of 25 ℃, the battery is at 4mAh/cm2Run at face volume of (a). Fig. 1 is a graph of the cell voltage over time, showing a severe short circuit voltage plateau as indicated by the arrow, indicating that the cycling stability is less than 80h/20 cycles without any treatment of the Zn foil. In addition, statistics show that the coulombic efficiency of Zn dissolution/deposition is about 99.40% before short-circuiting of the battery.
Example 1
Preparing a negative electrode: uniformly mixing 0.5g of ZIF-8 and 0.5g of NMP (N-methylpyrrolidone) in a homogenizer at 2000rpm, adding 0.5g of a 10 wt% PVDF NMP solution, and uniformly mixing at 2000 rpm; and then, uniformly coating the slurry on the surface of a cleaned Zn foil by using a coater to form a ZIF-8 composite coating named ZIF-8-PVDF-TB @ Zn, wherein FIG. 2 is a scanning electron microscope image of the ZIF-8 composite coating under different multiplying factors, as can be seen from a in FIG. 2, the ZIF-8 composite coating is good in uniformity, and as can be seen from b in FIG. 2, the ZIF-8 is microscopically spindle-shaped.
Assembling the battery: in the experiment, copper foil is used as a positive electrode, ZIF-8-PVDF-TB @ Zn is used as a negative electrode, and a diaphragm is AGM. Electrolyte solution: dissolving water as solvent, zinc sulfate as zinc salt and manganese sulfate as manganese salt in water, Zn2+Mn at a concentration of 1.8mol/L2+The concentration is 0.2 mol/L.
And (3) testing the battery: in an environment of 25 ℃, the battery is at 4mAh/cm2The battery voltage is shown in fig. 3 along with the time change curve, as shown in fig. 3, the negative electrode has no short circuit in the operation process of 440h, and the stability of the battery is far better than that of the blank sample of the comparative example 1. In addition, statistics show that the coulombic efficiency of Zn dissolution/deposition before cell shorting was about 99.64%, better than the blank sample (comparative example 1).
Example 2
Preparing a negative electrode: uniformly mixing 0.5g of ZIF-8 and 0.5g of NMP in a homogenizer at 2000rpm, adding 0.5g of NMP solution containing 10% of PVDF, and uniformly mixing at 2000 rpm; then, the slurry was uniformly coated on the surface of the cleaned Zn foil using a spin coater with a spin speed of 6000rpm for 30s, which was named ZIF-8-PVDF-XT6000@ Zn.
Assembling the battery: in the experiment, copper foil is used as an anode, ZIF-8-PVDF-XT6000@ Zn is used as a cathode, and a diaphragm is AGM. Electrolyte solution: dissolving water as solvent, zinc sulfate as zinc salt and manganese sulfate as manganese salt in water, Zn2+Mn at a concentration of 1.8mol/L2+The concentration is 0.2 mol/L.
And (3) testing the battery: in an environment of 25 ℃, the battery is at 4mAh/cm2Fig. 4 is a graph of the cell voltage as a function of time, and as shown in fig. 4, the negative electrode did not short-circuit during about 600 hours of operation, showing stability much better than that of the blank sample of comparative example 1. In addition, statistics indicate the coulombic efficiency of Zn dissolution/deposition in ZIF-8-PVDF-XT6000@ Zn electrodeAbout 99.82% better than the blank (comparative example 1) and ZIF-8-PVDF-TB @ Zn (example 1).
By comprehensively comparing comparative example 1 and examples 1-2, it can be seen that the ZIF-8 composite coating formed on the surface of the zinc negative electrode can be applied under a large surface capacity (4 mAh/cm)2) The circulation stability of the Zn negative electrode is remarkably improved, and the ZIF-8 composite coating prepared by adopting a spin-coating method is better in improvement effect on the Zn negative electrode based on the ZIF-8 composite coating slurry with the same dosage and composition.
Example 3
The difference from example 3 is that:
preparing a negative electrode: uniformly mixing 0.5g of ZIF-8 and 0.5g of NMP in a homogenizer at 2000rpm, adding 0.5g of NMP solution containing 10% of PVDF, and uniformly mixing at 2000 rpm; then, the slurry was uniformly coated on the surface of the cleaned Zn foil using a spin coater, wherein the spin speed was 2000rpm and the spin time was 60s, and was named ZIF-8-PVDF-XT2000@ Zn.
And (3) testing the battery: in an environment of 25 ℃, the battery is at 4mAh/cm2Fig. 5 is a graph of the cell voltage as a function of time, and as shown in fig. 5, the negative electrode did not short-circuit during about 520h of operation, showing stability much better than that of the blank sample of comparative example 1. In addition, statistics show that the coulombic efficiency of the dissolution/deposition of Zn in the ZIF-8-PVDF-XT2000@ Zn electrode is about 99.75%.
Comparative example 2
The difference from example 3 is that:
preparing a negative electrode: uniformly mixing 0.5g of ZIF-8 and 0.5g of NMP in a homogenizer at 2000rpm, adding 0.4g of NMP solution containing 10% of PVDF, and uniformly mixing at 2000 rpm; then, the slurry was uniformly coated on the surface of the cleaned Zn foil using a spin coater with a spin speed of 6000rpm for 30s, named ZIF-8-PVDF-XT6000-2@ Zn.
And (3) testing the battery: in an environment of 25 ℃, the battery is at 4mAh/cm2Fig. 6 is a graph of the cell voltage as a function of time, as shown in fig. 6, the negative electrode was short-circuited during about 300h of operation. In addition, statistics show that ZIF-8-PVDF-XT6000-2Coulombic efficiency of Zn dissolution/deposition in the @ Zn electrode was about 99.69%. Thus, it was demonstrated that, when the mass ratio of ZIF-8 to PVDF was too large, the stability of the coating was insufficient and the dendrite-suppressing effect was significantly reduced, as compared with the case where the mass ratio was 10: 1. It should be noted that, although the mass ratio of ZIF-8 to PVDF was too large to affect the stability of the coating, the run time and stability of the cell were still better than those of comparative example 1.
Comparative example 3
The difference from example 3 is that:
preparing a negative electrode: uniformly mixing 0.5g of ZIF-8 and 0.5g of NMP in a homogenizer at 2000rpm, adding 1.5g of NMP solution containing 10% of PVDF, and uniformly mixing at 2000 rpm; then, the slurry was uniformly coated on the surface of the cleaned Zn foil using a spin coater with a spin speed of 6000rpm for 30s, which was named ZIF-8-PVDF-XT6000@ Zn.
And (3) testing the battery: in an environment of 25 ℃, the battery is at 4mAh/cm2Fig. 7 is a graph of the cell voltage as a function of time, as shown in fig. 7, the negative electrode was short-circuited during about 110h of operation. In addition, statistics show that the coulombic efficiency of the dissolution/deposition of Zn in the ZIF-8-PVDF-XT6000-3@ Zn electrode is about 99.55%. It is thus demonstrated that the dendrite-inhibiting effect of the coating is reduced when the mass ratio of ZIF-8 to PVDF is too large to be 10: 1. At the same time, the cell voltage rises by about 20mV, which is caused by the higher PVDF fraction, resulting in a decrease in ionic conductivity.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. The zinc ion battery is characterized in that a ZIF-8 composite coating is arranged on the surface of a Zn cathode and/or on one side of a diaphragm close to the Zn cathode, and the composite coating comprises ZIF-8 and a binder.
2. The zinc-ion battery of claim 1, wherein the binder is PVDF.
3. The zinc-ion battery of claim 2, wherein the mass ratio of ZIF-8 to PVDF is (4-12): 1.
4. the zinc ion battery according to any one of claims 1 to 3, wherein the ZIF-8 composite coating has a thickness of 5 to 50 μm.
5. The zinc-ion battery of claim 4, wherein the ZIF-8 composite coating is formed using a spin coating method or a blade coating method,
optionally, the rotation speed of the spin coating is 1000-8000 rpm, and the spin coating time is 10-60 s.
6. The zinc-ion battery of claim 1 or 4, wherein the ZIF-8 is prepared by: mixing and reacting a zinc ion solution and a 2-methylimidazole solution; the reaction solution was subjected to centrifugal drying to obtain ZIF-8 particles.
7. The zinc-ion battery of claim 6, wherein the molar ratio of the zinc ions to the 2-methylimidazole is 1: (1-3); and/or the presence of a gas in the gas,
the solute of the zinc ion solution comprises at least one selected from zinc sulfate, zinc nitrate and zinc acetate.
8. The zinc-ion battery according to claim 1, wherein the zinc-ion battery is an aqueous battery.
9. A method for improving the cycle performance of a zinc negative electrode of a zinc ion battery is characterized by comprising the following steps:
and forming a ZIF-8 composite coating on the surface of the Zn negative electrode and/or on one side of the separator close to the Zn negative electrode, wherein the composite coating comprises ZIF-8 and a binder.
10. The method of claim 9, wherein the binder is PVDF,
optionally, the mass ratio of the ZIF-8 to the PVDF is (4-12): 1;
optionally, the thickness of the ZIF-8 composite coating is 5-50 μm;
optionally, the ZIF-8 composite coating is formed by a spin coating method or a blade coating method, and the blade coating thickness is 5-50 μm; the spin coating speed is 1000-8000 rpm, and the spin coating time is 10-60 s.
CN202111183724.0A 2021-10-11 2021-10-11 Zinc ion battery and method for improving zinc negative electrode cycle performance of zinc ion battery Pending CN114142032A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111183724.0A CN114142032A (en) 2021-10-11 2021-10-11 Zinc ion battery and method for improving zinc negative electrode cycle performance of zinc ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111183724.0A CN114142032A (en) 2021-10-11 2021-10-11 Zinc ion battery and method for improving zinc negative electrode cycle performance of zinc ion battery

Publications (1)

Publication Number Publication Date
CN114142032A true CN114142032A (en) 2022-03-04

Family

ID=80394177

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111183724.0A Pending CN114142032A (en) 2021-10-11 2021-10-11 Zinc ion battery and method for improving zinc negative electrode cycle performance of zinc ion battery

Country Status (1)

Country Link
CN (1) CN114142032A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115000411A (en) * 2022-08-05 2022-09-02 临沂华太电池有限公司 Alkaline battery cathode material for marine environment and battery using same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115000411A (en) * 2022-08-05 2022-09-02 临沂华太电池有限公司 Alkaline battery cathode material for marine environment and battery using same
CN115000411B (en) * 2022-08-05 2022-11-15 临沂华太电池有限公司 Alkaline battery cathode material for marine environment and battery using same

Similar Documents

Publication Publication Date Title
JP4368823B2 (en) Composite polymer electrolyte for lithium secondary battery containing lithium single ion conductive inorganic additive and method for producing the same
KR101761803B1 (en) Aqueous slurry for battery electrodes
US11211635B2 (en) Battery, battery pack, and uninterruptible power supply
JP2019526915A (en) Porous silicon material and conductive polymer binder electrode
CN110649313B (en) Lithium ion battery without diaphragm and preparation method thereof
CN109167063A (en) A kind of lithium anode and its preparation method and application of artificial solid electrolyte interface layer protection
CN115133222A (en) Double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, preparation method and lithium metal battery applying diaphragm
CN114551883A (en) Aqueous zinc ion battery coating, cathode and battery
CN114142032A (en) Zinc ion battery and method for improving zinc negative electrode cycle performance of zinc ion battery
US11545722B2 (en) Separators for electrochemical cells and methods of making the same
WO2023185944A1 (en) Electrolyte system free of free solvent molecules, preparation method therefor, and application thereof
WO2023134234A1 (en) Positive electrode composite material, preparation method therefor, positive electrode, and lithium ion secondary battery
KR100359605B1 (en) Lithium secondary battery cathode composition, lithium secondary battery cathode and lithium secondary battery employing the same, and method for preparing the same
CN116259735A (en) Negative electrode material, negative electrode sheet and battery
CN114262447B (en) Two-dimensional covalent organic framework material with cation framework, preparation method and application thereof, and lithium metal battery electrode
CN115548344A (en) Negative plate of battery without negative active material, preparation method thereof and battery
CN114665167A (en) Preparation method of organic ion/electron mixed conductor interface layer for stabilizing zinc metal cathode
CN109273670A (en) A kind of lithium anode and preparation method thereof with high-specific-surface mesoporous protective film
CN114203975A (en) Method for improving cycle performance of lithium metal battery
CN108987803B (en) Lithium metal negative electrode film-forming electrolyte for lithium-sulfur battery and additive thereof
KR100359054B1 (en) Metal oxide electrodes modified by conductive slurries and lithium secondary batteries
KR100432669B1 (en) Negative active material for rechargeable lithium batteries and preparing for same
CN109950484A (en) Prepare method, the anode, battery of rich lithium composite positive pole
CN116014086B (en) Negative electrode and preparation method and application thereof
US20230246195A1 (en) Inorganic binders for improved anodes in rechargeable alkali metal ion batteries

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20230406

Address after: 66 Tianshan Road, Xinbei District, Changzhou City, Jiangsu Province

Applicant after: Ruihai Bo (Changzhou) Energy Technology Co.,Ltd.

Address before: 93 crescent, Waterloo Valley ridge, Ontario

Applicant before: Chen Pu