CN113921810A - Ultrahigh-capacity zinc-cobalt battery positive electrode and self-activation preparation method thereof - Google Patents

Ultrahigh-capacity zinc-cobalt battery positive electrode and self-activation preparation method thereof Download PDF

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CN113921810A
CN113921810A CN202111182425.5A CN202111182425A CN113921810A CN 113921810 A CN113921810 A CN 113921810A CN 202111182425 A CN202111182425 A CN 202111182425A CN 113921810 A CN113921810 A CN 113921810A
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zinc
cobalt
battery
cobalt battery
capacity
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CN113921810B (en
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谈鹏
尚文旭
俞文涛
马彦义
何义
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive 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

Abstract

The invention discloses an ultrahigh-capacity zinc-cobalt battery anode and a self-activation preparation method thereof, belonging to the technical field of zinc-cobalt batteries, wherein the ultrahigh-capacity zinc-cobalt battery anode has a two-stage superfine nanosheet structure, the length of a first-stage nanosheet is 10 mu m, and the thickness of a second-stage superfine nanosheet is 1.7-6 nm; the anode of the zinc-cobalt battery is used in the zinc-cobalt battery, the discharge capacity of the battery can reach 402.5-482.2 mAh/g, the secondary superfine nanosheet structure of the anode of the ultra-high capacity zinc-cobalt battery creates an ultra-high specific surface with a large number of active sites and a porous structure which is beneficial to material and electron transmission and electrolyte permeation, the transfer capacity of electrons in the charging and discharging process is enhanced, and the discharge capacity of the anode used in the zinc-cobalt battery can reach 482.2 mAh/g.

Description

Ultrahigh-capacity zinc-cobalt battery positive electrode and self-activation preparation method thereof
Technical Field
The invention relates to the technical field of zinc-cobalt batteries, in particular to an ultrahigh-capacity zinc-cobalt battery anode and a self-activation preparation method thereof.
Background
The zinc-cobalt battery is a battery which takes metal zinc as a negative electrode, cobalt-based oxide as a positive electrode and takes neutral or alkaline aqueous solution as electrolyte. During discharge, the dissolution of metal zinc and the reduction reaction of cobalt-based oxide occur in the battery; while upon charging, deposition of metallic zinc and oxidation reaction of the cobalt-based oxide occur. Thus, the battery can be charged and discharged for many times. The zinc-cobalt battery has higher discharge voltage (1.8V), energy density of 500Wh/kg and good safety of electrode and electrolyte materials, and is considered to be a battery with great development potential.
Due to cobaltosic oxide (Co)3O4) Has higher theoretical capacity (446mAh/g) and is widely applied to the positive electrode of the zinc-cobalt battery. For the battery anode materials reported at present, such as cobaltosic oxide nanosheets (adv. mater.2016,28,4904), the actual discharge capacity is only 162mAh/g due to large size (270 nm) and poor conductivity; cobaltosic oxide nanoclusters (appl. cat. b-environ.2019,241,104) reach micron-sized (-5.7 μm) in size, but have poor wettability with electrolyte, resulting in an actual discharge capacity of only 173.6 mAh/g. The reason for limiting the capacity of the anode material of the zinc-cobalt battery mainly has two aspects: 1) the poor morphology structure causes the electrode to have small specific surface area and poor wettability with electrolyte; 2) the valence state utilization capability is poor, and the space for converting to a low valence state and a high valence state in the charging and discharging process is small, so that the electron transfer capability is insufficient.
Disclosure of Invention
In order to solve the problem of low actual capacity caused by low utilization rate of the zinc-cobalt battery anode material, the invention provides an ultrahigh-capacity zinc-cobalt battery anode and a self-activation preparation method thereof, which can realize high electrochemical performance of the battery.
In order to achieve the purpose, the invention provides the following scheme:
the ultrahigh-capacity zinc-cobalt battery positive electrode has a two-stage superfine nanosheet structure, wherein the length of a first-stage nanosheet is 10 mu m, and the thickness of a second-stage superfine nanosheet is 1.7-6 nm; the zinc-cobalt battery anode has excellent valence conversion capacity: the positive electrode of the zinc-cobalt battery is used in the zinc-cobalt battery, and the discharge capacity of the battery can reach 402.5-482.2 mAh/g.
The invention provides a self-activation preparation method of a cathode of an ultrahigh-capacity zinc-cobalt battery, which comprises the following steps:
(1) assembling the traditional cobaltosic oxide nanosheet electrode into a zinc-cobalt battery with air holes;
(2) charging and discharging the zinc-cobalt battery at a current density of 3.0A/g;
(3) and (3) cycling the charging and discharging conditions in the step (2) for 100-200 times to obtain the activated ultrahigh-capacity zinc-cobalt battery electrode.
Further, the preparation method of the traditional cobaltosic oxide nanosheet electrode comprises the following steps:
dissolving cobalt nitrate hexahydrate, ammonium fluoride and urea in deionized water, and stirring to prepare a precursor solution; placing the foamed nickel current collector in a precursor solution, and carrying out hydrothermal reaction to prepare a current collector loaded with a precursor; and cleaning, drying and calcining the current collector carrying the precursor, and cooling the current collector to room temperature along with the furnace.
Further, the molar ratio of the cobalt nitrate hexahydrate to the ammonium fluoride to the urea is 1: 9: 16.
further, the hydrothermal reaction temperature is 120 ℃ and the time is 9 hours.
Further, the drying temperature is 60 ℃, and the drying time is 3 hours; the heating rate is 1 ℃/min, the calcining temperature is 350 ℃, and the calcining time is 3 hours.
Further, the cobaltosic oxide loading capacity on the traditional cobaltosic oxide nanosheet electrode is 2.2mg/cm2。
Preferably, the preparation method of the conventional cobaltosic oxide nanosheet electrode comprises the following steps: dissolving 0.5mmol of cobalt nitrate hexahydrate, 4.5mmol of ammonium fluoride and 8mmol of urea in 40mL of deionized water, stirring for 5 minutes to prepare a precursor solution, and pouring the precursor solution into a 50mL hydrothermal kettle with a polytetrafluoroethylene lining; placing the foamed nickel current collector into a hydrothermal kettle, completely submerging the foamed nickel current collector into a precursor solution, sealing the hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 9 hours to obtain a current collector loaded with a precursor(ii) a Cleaning a current collector loaded with a precursor, drying the current collector for 3 hours at the temperature of 60 ℃, placing the current collector in a muffle furnace, heating the current collector to 350 ℃ at the heating rate of 1 ℃/min, calcining the current collector in air for 3 hours, cooling the current collector to room temperature along with the furnace, and obtaining an electrode with the capacity of cobaltosic oxide of 2.2mg/cm2。
Furthermore, the zinc-cobalt battery with the air holes has the air permeability of 70-80%.
Further, the charging and discharging time in the charging and discharging process was 15 minutes each.
Further, the cut-off voltage is not limited in the charge and discharge process.
The electrochemical principle involved in the invention is as follows:
1) because the voltage range is not limited and the battery is provided with the air holes, the gas exchange can be effectively carried out between the inside and the outside of the cavity of the zinc-cobalt battery with the air holes, so that the battery can run from the zinc-cobalt reaction section to the zinc-oxygen reaction section, and the cavity of the battery is ensured not to bulge in the charging process. Unlike conventional charge and discharge protocols (i.e., operating in the presence of a cut-off voltage), the cobaltosic oxide electrode can be fully charged at high voltages and fully discharged at low voltages. Thus, the ability to switch between higher and lower valence states may be continually increased with repeated cycling. Conversely, discharge cycling at a finite cutoff voltage may limit the utilization of valence states;
2) because oxygen precipitation reaction is involved in the charging and discharging processes of the zinc-oxygen reaction section, the electrolyte on the surface of the electrode is more uniformly distributed due to continuous generation and release of oxygen, and the wettability between the electrode and the electrolyte is improved;
3) the improvement in wettability allows the electrode material to be in sufficient contact with the electrolyte during the reaction. The agglomerated particles in the pristine nanosheets spontaneously change toward a high specific surface area, wherein a secondary ultrafine nanosheet structure having a variety of pore structures is produced.
The beneficial technical effects of the invention are embodied in the following three aspects:
1) the appearance structure is as follows: the two-stage superfine nanosheet structure of the anode of the ultrahigh-capacity zinc-cobalt battery creates an ultrahigh specific surface with a large number of active sites and a porous structure beneficial to species and electron transmission and electrolyte permeation;
2) valence conversion ability: the ultrahigh valence state conversion capacity of the anode of the ultrahigh-capacity zinc-cobalt battery enhances the transfer capacity of electrons in the charging and discharging processes;
3) ultra-high capacity: the cathode of the ultra-high capacity zinc-cobalt battery is used in the zinc-cobalt battery, and the discharge capacity can reach 482.2 mAh/g.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a low-magnification microscopic morphology image of a scanning electron microscope of the anode of the ultra-high capacity zinc-cobalt battery prepared in example 1;
FIG. 2 is a high-power microscopic morphology image of the scanning electron microscope of the anode of the ultra-high capacity zinc-cobalt battery prepared in example 1;
FIG. 3 is a low-power microscopic morphology image of the positive electrode of the ultra-high capacity zinc-cobalt battery prepared in example 1 by using a transmission electron microscope;
FIG. 4 is a high-power microscopic morphology image of the positive electrode of the ultra-high capacity zinc-cobalt battery prepared in example 1 by using a transmission electron microscope;
FIG. 5 is a graph of the charge-discharge voltage during self-activation of the Zn-Co battery of example 1;
FIG. 6 is a graph showing the charging and discharging voltage curves of a zinc-cobalt battery assembled by applying the cathode of the ultra-high capacity zinc-cobalt battery prepared in example 1;
FIG. 7 is a low-magnification microscopic morphology image of the scanning electron microscope of the anode of the ultra-high capacity zinc-cobalt battery prepared in example 2;
FIG. 8 is a high-magnification microscopic morphology image of the scanning electron microscope of the anode of the ultra-high capacity zinc-cobalt battery prepared in example 2;
FIG. 9 is a low-power microscopic morphology image of the positive electrode of the ultra-high capacity zinc-cobalt battery prepared in example 2 by using a transmission electron microscope;
FIG. 10 is a high-power microscopic morphology image of the positive electrode of the ultra-high capacity zinc-cobalt battery prepared in example 2 by using a transmission electron microscope;
FIG. 11 is a graph of the charge and discharge voltage during self-activation of the Zn-Co battery of example 2;
fig. 12 is a charge-discharge voltage curve diagram of a zinc-cobalt battery assembled by applying the cathode of the ultra-high capacity zinc-cobalt battery prepared in example 2.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The assembling method of the zinc-cobalt battery is a conventional technical means in the field, is not the main point of the invention, and is not described herein.
Example 1
A self-activation preparation method of a positive electrode of an ultrahigh-capacity zinc-cobalt battery comprises the following steps:
(1) assembling a traditional cobaltosic oxide electrode into a zinc-cobalt battery with 75% of air permeability, wherein the preparation method of the traditional cobaltosic oxide nanosheet electrode comprises the following steps: dissolving 0.5mmol of cobalt nitrate hexahydrate, 4.5mmol of ammonium fluoride and 8mmol of urea in 40mL of deionized water, stirring for 5 minutes to prepare a precursor solution, and pouring the precursor solution into a 50mL hydrothermal kettle with a polytetrafluoroethylene lining; placing the foamed nickel current collector in a hydrothermal kettle, completely submerging the foamed nickel current collector in a precursor solution, sealing the hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 9 hours to obtain a current collector loaded with a precursor; cleaning a current collector loaded with a precursor, drying the current collector for 3 hours at the temperature of 60 ℃, placing the current collector in a muffle furnace, heating the current collector to 350 ℃ at the heating rate of 1 ℃/min, calcining the current collector in air for 3 hours, cooling the current collector to room temperature along with the furnace, and obtaining an electrode with the capacity of cobaltosic oxide of 2.2mg/cm2；
(2) The zinc-cobalt battery is charged and discharged at a current density of 3.0A/g, and the charging and discharging time is 15 minutes respectively;
(3) and (3) performing self-activation circulation for 200 times under the charging and discharging conditions of the step (2) to obtain the anode.
The positive electrode of the ultra-high capacity zinc-cobalt battery prepared by the embodiment is shown in a scanning electron microscope low-power micro-topography map in figure 1, a scanning electron microscope high-power micro-topography map in figure 2, a transmission electron microscope low-power micro-topography map in figure 3 and a transmission electron microscope high-power micro-topography map in figure 4. Referring to fig. 1, 2, 3 and 4, the material obtained in this embodiment is a material with a multi-stage nanosheet structure, and the first-stage nanosheet structure is uniformCovering the surface of the foamed nickel, wherein the length of the foamed nickel is 10 mu m, and the thickness of the second-stage superfine nano sheet is 1.7 nm. The charge-discharge voltage curve chart of the zinc-cobalt battery in the self-activation process of the embodiment is shown in figure 5, and after 200 self-activation cycles, the discharge capacity of the zinc-cobalt segment of the zinc-cobalt battery is 0.58mAh/cm2Increased to 1.31mAh/cm2。
Assembling and testing the battery: the cathode of the battery adopts a zinc plate with the purity of more than 99% and the thickness of 0.5mm, the electrolyte adopts an alkaline aqueous solution prepared by mixing 6mol/L potassium hydroxide, 0.2mol/L zinc acetate and deionized water, and the anode of the battery is the anode of the ultra-high capacity zinc-cobalt battery prepared in the embodiment. The charge-discharge cut-off voltage range is set to be 1.4-1.9V, the charge-discharge voltage curve chart of the zinc-cobalt battery assembled by the ultra-high capacity zinc-cobalt battery anode prepared by the embodiment is shown in figure 6, and as can be seen from figure 6, under the condition that the discharge current is 0.5A/g, the discharge capacity is increased to 482.2mAh/g from 219.2 mAh/g.
Example 2
A self-activation preparation method of a positive electrode of an ultrahigh-capacity zinc-cobalt battery comprises the following steps:
(1) assembling a traditional cobaltosic oxide electrode into a zinc-cobalt battery with 75% of air permeability, wherein the preparation method of the traditional cobaltosic oxide electrode is the same as that of the embodiment 1;
(2) the zinc-cobalt battery is charged and discharged at a current density of 3.0A/g, and the charging and discharging time is 15 minutes respectively;
(3) and (3) performing self-activation circulation for 100 times under the charging and discharging conditions in the step (2) to obtain the ultrahigh-capacity zinc-cobalt battery electrode.
The positive electrode scanning electron microscope macroscopic microstructure picture of the ultra-high capacity zinc-cobalt battery prepared by the embodiment is shown in figure 7, the scanning electron microscope macroscopic microstructure picture is shown in figure 8, the transmission electron microscope macroscopic microstructure picture is shown in figure 9, and the transmission electron microscope macroscopic microstructure picture is shown in figure 10. The material with the multilevel nanosheet structure is obtained in the embodiment, the first-level nanosheet structure uniformly covers the surface of the foamed nickel, the length of the first-level nanosheet structure is 10 microns, and the thickness of the second-level ultrafine nanosheet structure is 6 nm. The charge-discharge voltage curve chart of the zinc-cobalt battery in the self-activation process of the embodiment is shown in fig. 11, and after 100 self-activation cycles, the discharge capacity of the zinc-cobalt section of the zinc-cobalt batteryThe amount is 0.58mAh/cm2Increased to 1.03mAh/cm2。
Assembling and testing the battery: the cathode of the battery adopts a zinc plate with the purity of more than 99% and the thickness of 0.5mm, the electrolyte adopts an alkaline aqueous solution prepared by mixing 6mol/L potassium hydroxide, 0.2mol/L zinc acetate and deionized water, and the anode of the battery is the anode of the ultra-high capacity zinc-cobalt battery prepared in the embodiment. The charge-discharge cut-off voltage range is set to be 1.4-1.9V, a charge-discharge voltage curve chart of the zinc-cobalt battery assembled by the ultra-high capacity zinc-cobalt battery prepared by the embodiment is shown in figure 12, and the discharge capacity is increased from 219.2mAh/g to 402.5mAh/g under the condition that the discharge current is 0.5A/g.
Example 3
A self-activation preparation method of a positive electrode of an ultrahigh-capacity zinc-cobalt battery comprises the following steps:
(1) assembling a traditional cobaltosic oxide electrode into a zinc-cobalt battery with 75% of air permeability, wherein the preparation method of the traditional cobaltosic oxide electrode is the same as that of the embodiment 1;
(2) the zinc-cobalt battery is charged and discharged at a current density of 3.0A/g, and the charging and discharging time is 15 minutes respectively;
(3) and (3) performing self-activation circulation for 150 times under the charging and discharging conditions in the step (2) to obtain the ultrahigh-capacity zinc-cobalt battery electrode.
The material with the multilevel nanosheet structure is obtained in the embodiment, the first-level nanosheet structure uniformly covers the surface of the foamed nickel, the length of the first-level nanosheet structure is 10 microns, and the thickness of the second-level ultrafine nanosheet structure is 4 nm. After 150 times of self-activation cycles, the discharge capacity of the zinc-cobalt segment is 0.58mAh/cm2Increased to 1.23mAh/cm2。
The battery assembly and test conditions were the same as in example 1, except that the ultra-high capacity zinc-cobalt battery electrode prepared in this example was used as the positive electrode of the zinc-cobalt battery. The charge-discharge cut-off voltage range is set to be 1.4-1.9V, and the discharge capacity is increased from 219.2mAh/g to 455.7mAh/g under the condition that the discharge current is 0.5A/g.
Example 4
A self-activation preparation method of a positive electrode of an ultrahigh-capacity zinc-cobalt battery comprises the following steps:
(1) assembling a traditional cobaltosic oxide electrode into a zinc-cobalt battery with 70% of air permeability, wherein the preparation method of the traditional cobaltosic oxide electrode is the same as that of the embodiment 1;
(2) the zinc-cobalt battery is charged and discharged at a current density of 3.0A/g, and the charging and discharging time is 15 minutes respectively;
(3) and (3) performing self-activation circulation for 120 times under the charging and discharging conditions of the step (2) to obtain the ultrahigh-capacity zinc-cobalt battery electrode.
The material with the multilevel nanosheet structure is obtained in the embodiment, the first-level nanosheet structure uniformly covers the surface of the foamed nickel, the length of the first-level nanosheet structure is 10 microns, and the thickness of the second-level ultrafine nanosheet structure is 5 nm. After 120 times of self-activation cycles, the discharge capacity of the zinc-cobalt segment is 0.58mAh/cm2Increased to 1.11mAh/cm2。
The battery assembly and test conditions were the same as in example 1, except that the ultra-high capacity zinc-cobalt battery electrode prepared in this example was used as the positive electrode of the zinc-cobalt battery. The charge-discharge cut-off voltage range is set to be 1.4-1.9V, and the discharge capacity is increased from 219.2mAh/g to 423.8mAh/g under the condition that the discharge current is 0.5A/g.
Example 5
A self-activation preparation method of a positive electrode of an ultrahigh-capacity zinc-cobalt battery comprises the following steps:
(1) assembling a traditional cobaltosic oxide electrode into a zinc-cobalt battery with the air permeability of 80%, wherein the preparation method of the traditional cobaltosic oxide electrode is the same as that of the embodiment 1;
(2) the zinc-cobalt battery is charged and discharged at a current density of 3.0A/g, and the charging and discharging time is 15 minutes respectively;
(3) and (3) performing self-activation circulation for 180 times under the charging and discharging conditions of the step (2) to obtain the ultrahigh-capacity zinc-cobalt battery electrode.
The material with the multilevel nanosheet structure is obtained in the embodiment, the first-level nanosheet structure uniformly covers the surface of the foamed nickel, the length of the first-level nanosheet structure is 10 microns, and the thickness of the second-level ultrafine nanosheet structure is 3 nm. After 180 times of self-activation circulation, the discharge capacity of the zinc-cobalt segment is 0.58mAh/cm2Increased to 1.28mAh/cm2。
The battery assembly and test conditions were the same as in example 1, except that the ultra-high capacity zinc-cobalt battery electrode prepared in this example was used as the positive electrode of the zinc-cobalt battery. The charge-discharge cut-off voltage range is set to be 1.4-1.9V, and the discharge capacity is increased from 219.2mAh/g to 473.5mAh/g under the condition that the discharge current is 0.5A/g.
Comparative example 1
A self-activation preparation method of a positive electrode of an ultrahigh-capacity zinc-cobalt battery comprises the following steps:
(1) assembling a traditional cobaltosic oxide electrode into a zinc-cobalt battery with 75% of air permeability, wherein the preparation method of the traditional cobaltosic oxide electrode is the same as that of the embodiment 1;
(2) the zinc-cobalt battery is charged and discharged at a current density of 3.0A/g, and the charging and discharging time is 15 minutes respectively;
(3) and (3) performing self-activation circulation for 50 times under the charging and discharging conditions of the step (2) to obtain the ultrahigh-capacity zinc-cobalt battery electrode.
The electrode of the ultrahigh-capacity zinc-cobalt battery obtained by the comparative example has a single-stage nanosheet structure and a length of 10 micrometers. After 50 times of self-activation circulation, the discharge capacity of the zinc-cobalt segment is 0.58mAh/cm2Increased to 0.80mAh/cm2。
The battery assembly and test conditions were the same as in example 1, except that the ultra-high capacity zinc-cobalt battery electrode prepared in this example was used as the positive electrode of the zinc-cobalt battery. The charge-discharge cut-off voltage range is set to be 1.4-1.9V, and the discharge capacity is increased from 219.2mAh/g to 300.4mAh/g under the condition that the discharge current is 0.5A/g.
Comparative example 2
The traditional cobaltosic oxide electrode is directly used as a positive electrode to be assembled into a zinc-cobalt battery, the battery assembling and testing conditions are the same as those in example 1, and the electrode of the ultrahigh-capacity zinc-cobalt battery obtained by the comparative example has a single-stage nanosheet structure and is 10 micrometers in length. The charge-discharge cut-off voltage range is set to be 1.4-1.9V, and the discharge capacity is always maintained to be about 219.2mAh/g under the condition that the discharge current is 0.5A/g.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (5)

1. The ultrahigh-capacity zinc-cobalt battery anode is characterized by having a two-stage superfine nanosheet structure, wherein the length of a first-stage nanosheet is 10 microns, and the thickness of a second-stage superfine nanosheet is 1.7-6 nm; the positive electrode of the zinc-cobalt battery is used in the zinc-cobalt battery, and the discharge capacity of the battery reaches 402.5-482.2 mAh/g.
2. The self-activation preparation method of the ultra-high capacity zinc-cobalt battery positive electrode as claimed in claim 1, characterized by comprising the following steps:
(1) assembling the traditional cobaltosic oxide nanosheet electrode into a zinc-cobalt battery with air holes;
(2) charging and discharging the zinc-cobalt battery at a current density of 3.0A/g;
(3) and (3) circulating the charging and discharging conditions in the step (2) for 100-200 times to obtain the ultrahigh-capacity zinc-cobalt battery electrode.
3. The self-activating preparation method according to claim 2, wherein the zinc-cobalt battery with the air holes has an air permeability of 70-80%.
4. The self-activation preparation method according to claim 2, wherein the charge and discharge time in the charge and discharge process is 15 minutes each.
5. The self-activation production method according to claim 2, wherein a cut-off voltage is not limited during the charge and discharge.
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1176649A1 (en) * 2000-07-24 2002-01-30 Sociedad Espanola Del Acumulador Tudor, S.A. An alkaline secondary battery with an improved positive nickel electrode and procedure for its activation
CN101692491A (en) * 2009-09-22 2010-04-07 哈尔滨工业大学 Preparation method of three-dimensional foamed cobalt oxide cathode
CN107742584A (en) * 2017-08-25 2018-02-27 江苏大学 One seed nucleus nucleocapsid trielement composite material Co3O4/PANI/MnO2Preparation method and use
CN107785542A (en) * 2016-08-29 2018-03-09 南京安普瑞斯有限公司 A kind of lithium ion battery with high energy density and preparation method
CN107946547A (en) * 2017-11-16 2018-04-20 燕山大学 A kind of in-situ preparation method of high-energy-density cobalt hydroxide film electrode
CN109802093A (en) * 2019-01-21 2019-05-24 深圳大学 Modified non-carbon anode of lithium-air battery and preparation method thereof and lithium-air battery
CN110098448A (en) * 2019-05-28 2019-08-06 中国科学技术大学 A kind of high-performance composite zinc air secondary battery
CN110498413A (en) * 2019-08-27 2019-11-26 中南大学 A kind of orientation regulation porous active Carbon Materials aperture and graphitizing method and its application in lithium-ion capacitor
CN111129439A (en) * 2020-01-15 2020-05-08 中国科学技术大学 High-performance zinc-cobalt battery positive electrode and preparation method thereof
CN111584250A (en) * 2020-05-14 2020-08-25 淮南师范学院 Preparation method of foamed nickel loaded praseodymium-doped cobaltosic oxide supercapacitor electrode material
CN112436203A (en) * 2020-12-28 2021-03-02 中国科学技术大学 Charging method for reducing self-discharge of zinc-cobalt battery
CN113457679A (en) * 2020-03-31 2021-10-01 中国科学院宁波材料技术与工程研究所 Preparation method and application of cobalt oxyhydroxide catalyst

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1176649A1 (en) * 2000-07-24 2002-01-30 Sociedad Espanola Del Acumulador Tudor, S.A. An alkaline secondary battery with an improved positive nickel electrode and procedure for its activation
CN101692491A (en) * 2009-09-22 2010-04-07 哈尔滨工业大学 Preparation method of three-dimensional foamed cobalt oxide cathode
CN107785542A (en) * 2016-08-29 2018-03-09 南京安普瑞斯有限公司 A kind of lithium ion battery with high energy density and preparation method
CN107742584A (en) * 2017-08-25 2018-02-27 江苏大学 One seed nucleus nucleocapsid trielement composite material Co3O4/PANI/MnO2Preparation method and use
CN107946547A (en) * 2017-11-16 2018-04-20 燕山大学 A kind of in-situ preparation method of high-energy-density cobalt hydroxide film electrode
CN109802093A (en) * 2019-01-21 2019-05-24 深圳大学 Modified non-carbon anode of lithium-air battery and preparation method thereof and lithium-air battery
CN110098448A (en) * 2019-05-28 2019-08-06 中国科学技术大学 A kind of high-performance composite zinc air secondary battery
CN110498413A (en) * 2019-08-27 2019-11-26 中南大学 A kind of orientation regulation porous active Carbon Materials aperture and graphitizing method and its application in lithium-ion capacitor
CN111129439A (en) * 2020-01-15 2020-05-08 中国科学技术大学 High-performance zinc-cobalt battery positive electrode and preparation method thereof
CN113457679A (en) * 2020-03-31 2021-10-01 中国科学院宁波材料技术与工程研究所 Preparation method and application of cobalt oxyhydroxide catalyst
CN111584250A (en) * 2020-05-14 2020-08-25 淮南师范学院 Preparation method of foamed nickel loaded praseodymium-doped cobaltosic oxide supercapacitor electrode material
CN112436203A (en) * 2020-12-28 2021-03-02 中国科学技术大学 Charging method for reducing self-discharge of zinc-cobalt battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
朱刚等: "Co3O4纳米片的制备及其电化学性能", 《化工新型材料》 *
杜晓军等: "Co3O4/Ni泡沫复合材料的制备及其在超级电容器的应用研究", 《现代化工》 *

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