CN113871620A - Ultrathin interface modified zinc metal negative electrode material, and preparation and application thereof - Google Patents

Ultrathin interface modified zinc metal negative electrode material, and preparation and application thereof Download PDF

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CN113871620A
CN113871620A CN202110956730.9A CN202110956730A CN113871620A CN 113871620 A CN113871620 A CN 113871620A CN 202110956730 A CN202110956730 A CN 202110956730A CN 113871620 A CN113871620 A CN 113871620A
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zinc
negative electrode
deposited
protective layer
functionalized graphene
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谢嫚
周佳辉
吴锋
夏信德
郝宇童
张壹心
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He'nan Penghui Power Supply Co ltd
Beijing Institute of Technology BIT
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He'nan Penghui Power Supply Co ltd
Beijing Institute of Technology BIT
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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
    • H01M4/38—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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/026—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

Abstract

The invention relates to an ultrathin interface modified zinc metal negative electrode material, and preparation and application thereof, and belongs to the technical field of zinc ion batteries. The negative electrode material is a zinc-containing metal material with a functionalized graphene protective layer with the thickness of 20 nm-3 mu m deposited on the surface, the functionalized graphene is graphene doped with N, P or S heteroatom, and the mass percentage of the doped heteroatom is 1% -3%; the functionalized graphene protective layer has uniform zinc deposition morphology and excellent conductivity, can reduce polarization of an electrode and effectively inhibit growth of zinc dendrites, effectively improves electrochemical performance of a zinc ion battery, and has good application prospect when being used as a cathode material of a water system zinc ion battery. The anode material is characterized in that a uniform ultrathin interface is constructed on the surface of zinc metal by a vertical lifting synthesis method, and the preparation process is simple, green, environment-friendly, low in cost and easy to popularize.

Description

Ultrathin interface modified zinc metal negative electrode material, and preparation and application thereof
Technical Field
The invention relates to an ultrathin interface modified zinc metal negative electrode material, and preparation and application thereof, and belongs to the technical field of zinc ion batteries.
Background
The increasing demand of renewable energy sources promotes the development of high-safety, stable, low-cost and environment-friendly electrochemical energy storage systems. Zinc is a cheap and abundant metal, and has high volume capacity (5855 mAh/cm)3) And a lower redox potential (-0.76V versus standard hydrogen electrode), aqueous zinc-ion batteries are one of the candidates for next generation energy storage devices due to the advantages of the zinc metal negative electrode itself. In recent years, various aqueous zinc-based batteries, such as Zn-MnO2、Zn-V2O5、Zn-LiMn2O4Systems and the like have been widely studied and made important progress. However, these problems lead to unstable interfaces due to the tendency of deposition to dendritic growth due to non-uniform nucleation of the zinc negative electrode and severe hydrogen corrosion under thermodynamic push, thus severely hampering the large-scale application of aqueous zinc-ion batteries.
To solve these problems and achieve long-life zinc metal anodes, researchers have proposed many research approaches including interface modification, three-dimensional structure design, and high-concentration electrolytes. The interface modification can not only effectively prevent corrosion, but also is one of effective measures for regulating and controlling the growth of dendrites. Early interfacial modification mostly used a doctor blade coating method to obtain a non-dendritic composite negative electrode (e.g., Advanced Low-Cost, High-Voltage, Long-Life Aqueous Hybrid Source/Zinc Batteries Enabled by a Dendrite-Free Zinc acid and centralized Electrolyte, Jiang Kai, ACS applied. Material. interfaces,2018,10,26, 22059. 22066.). However, this simple approach relies heavily on the use of binders and does not produce ultra-thin coatings (<10 μm), with thicker coatings on the electrodes both reducing the energy density and increasing the resistance of the electrolyte-electrode interface.
The nano-scale interface modification can complete faster kinetic energy transmission under lower interface impedance, and can produce a high specific energy metal cathode capable of prolonging the cycle. Recently, techniques such as atomic layer deposition and chemical vapor deposition are used to modify Zn anodes and achieve ultra-thin interface modification. Although the technologies realize the ultrathin interface modification of the Zn anode, the preparation cost is high, the requirement on the preparation condition is high, and the application of the ultrathin interface modified zinc metal negative electrode material is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an ultrathin interface modified zinc metal negative electrode material, and preparation and application thereof, wherein the negative electrode material is zinc-containing metal with an ultrathin functionalized graphene protective layer deposited on the surface, the protective layer has uniform zinc deposition morphology and excellent conductivity, can reduce the polarization of an electrode and effectively inhibit the growth of zinc dendrites, effectively improves the electrochemical performance of a zinc ion battery, and has good application prospect when being used as a negative electrode material of a water system zinc ion battery; the anode material is characterized in that a uniform ultrathin interface is constructed on the surface of zinc metal by a vertical lifting synthesis method, and the preparation process is simple, green, environment-friendly, low in cost and easy to popularize.
The purpose of the invention is realized by the following technical scheme.
The zinc metal negative electrode material modified by the ultrathin interface is a zinc metal material with a functionalized graphene protective layer deposited on one surface;
the thickness of the functionalized graphene protective layer is 20 nm-3 mu m, the functionalized graphene is graphene doped with N, P or S heteroatom, and the mass percentage of the doped heteroatom is 1% -3%.
Further, the zinc-containing metal material is a zinc foil or a zinc alloy foil.
Further, the thickness of the functionalized graphene protective layer is 50nm to 1 μm, more preferably 80nm to 200 nm.
The preparation method of the ultrathin interface modified zinc metal negative electrode material comprises the following specific steps:
(1) adding the functionalized graphene material into an alcohol solvent to prepare slurry with the concentration of 1 mg/mL-5 mg/mL;
further, the alcohol solvent is methanol, ethanol or ethylene glycol;
further, the functionalized graphene material is prepared by the following method:
calcining graphene oxide at 550-650 ℃ for 1-5 h in an ammonia atmosphere to obtain a nitrogen-doped graphene material;
concentrated phosphoric acid (mass fraction 85% -86%) and graphene oxide are mixed according to a ratio of 1 mL: (100-300) mg, and calcining at 550-650 ℃ for 1-5 h under the protection of inert gas atmosphere to obtain a phosphorus-doped graphene material;
mixing graphene oxide and benzyl disulfide according to the mass ratio of 1-5: 1, and calcining for 1-5 h at the temperature of 550-650 ℃ under the protection of an inert gas atmosphere to obtain a sulfur-doped graphene material;
(2) removing an oxide film on the surface to be deposited of the zinc-containing metal material, vertically immersing the zinc-containing metal material (namely, the surface to be deposited of the zinc-containing metal material is vertical to the bottom surface of a container) into the container containing water, dropwise adding the slurry prepared in the step (1) into the container from one side of the container opposite to the surface to be deposited of the zinc-containing metal material at the speed of 0.01-2 mL/s, vertically and upwardly pulling the zinc-containing metal material at the speed of 0.5-10 mm/s when the slurry is spread on the water surface and the slurry is spread on the surface to be deposited of the zinc-containing metal material, depositing a functionalized graphene protective layer on the surface to be deposited of the zinc-containing metal material pulled out from the solution, and directly wiping and removing the zinc-containing metal material if functionalized graphene is not deposited on the other surface of the zinc-containing metal material locally;
further, sanding the surface to be deposited of the zinc-containing metal material by using 1000-4000 meshes of abrasive paper, removing an oxide film on the surface of the zinc-containing metal material, and enabling the surface of the zinc-containing metal material to be smooth and flat;
(3) vertically immersing the metal-containing material deposited with the functionalized graphene protective layer obtained in the step (2) into a container filled with water, repeating the lifting operation in the step (2), repeatedly depositing the functionalized graphene protective layer on the functionalized graphene protective layer deposited on the surface of the metal-containing material until the required thickness is reached, and finally drying to obtain the cathode material;
further, drying at 60-80 ℃ to obtain the negative electrode material;
further, the concentration of the slurry is 1 mg/mL-5 mg/mL, the dropping speed of the slurry is 0.2 mL/s-1 mL/s, and the pulling speed of the zinc-containing metal material is 1 mm/s-3 mm/s.
According to the application of the ultrathin interface modified zinc metal cathode material, when the cathode material is applied to a water-based zinc ion battery, one surface of the cathode material deposited with a functionalized graphene protective layer is in contact with an electrolyte.
Has the advantages that:
(1) in the zinc metal negative electrode material modified by the ultrathin interface, the functional graphene protective layer deposited on the surface of the zinc-containing metal material has ultrathin thickness, abundant nucleation sites and excellent conductivity, so that on one hand, the contact area of the zinc metal negative electrode material and a water system electrolyte can be reduced, and the corrosion and dendrite effect of the zinc metal negative electrode material during long circulation can be avoided; on one hand, the polarization of the electrode can be reduced, and the electrochemical performance of the zinc ion battery can be effectively improved; on one hand, the heteroatom-doped graphene has larger adhesion with a zinc-containing metal material, so that the interface impedance is reduced, and the transmission dynamics is improved; on one hand, the zinc ion nucleating agent can guide the nucleation of zinc ions, is beneficial to the deposition of metal zinc and inhibits the growth of zinc dendrites, and has good application prospect when being used as a negative electrode material of a water system zinc ion battery.
(2) According to the invention, in the process of preparing the ultrathin interface modified zinc metal cathode material by adopting the vertical pulling method, the appearance and the thickness of the interface protective layer are effectively regulated and controlled by strictly controlling the slurry concentration, the slurry dropping speed and the zinc-containing metal material pulling speed, and the ultrathin and uniformly deposited functionalized graphene protective layer is successfully realized on the surface of the zinc-containing metal material. Particularly, the slurry concentration is strictly regulated and controlled, the slurry concentration is too high, graphene cannot be well spread in a container containing water, and the slurry concentration is too low, so that uniform deposition cannot be realized.
(3) The too thick thickness of the functionalized graphene protective layer can block the shuttle of zinc ions, increase the transmission path of the zinc ions and improve the polarization of the zinc ion battery; if the thickness of the functionalized graphene protection layer is too thin, the deposition of the functionalized graphene protection layer is not uniform. Moreover, the thickness of the functionalized graphene protective layer and the number of times of pulling are not in a simple linear relationship, and the bonding force between layers is weakened along with the increase of the number of times of pulling. Therefore, in order to ensure uniform deposition of the functionalized graphene protective layer and achieve good electrochemical performance, the thickness of the functionalized graphene protective layer needs to be reasonably regulated.
(4) The invention adopts the vertical pulling method to prepare the ultrathin interface modified zinc metal cathode material, and has the advantages of simple preparation process, easy operation, environmental protection, low cost and easy popularization.
Drawings
FIG. 1 is a photograph of NGO @ Zn prepared in example 1.
Figure 2 is a SEM (scanning electron microscope) image of the surface of the NGO @ Zn side deposited with the NGO overcoat layer prepared in example 1.
Figure 3 is a cross-sectional SEM image of NGO @ Zn prepared in example 1.
FIG. 4 is a graph of the current density at 1mA/cm for the assembled counter cell of example 12The capacity is 1mAh/cm2Cyclic performance graph of time.
FIG. 5 is a graph showing the current density of 1mA/cm for a cell assembled in comparative example 12The capacity is 1mAh/cm2Cyclic performance graph of time.
FIG. 6 is a graph showing the current density of 1mA/cm for a cell assembled in comparative example 12The capacity is 1mAh/cm2SEM image of electrode after 100 weeks of lower cycle.
FIG. 7 is a graph of the current density at 1mA/cm for a cell assembled in example 12The capacity is 1mAh/cm2SEM image of electrode after 100 weeks of lower cycle.
Fig. 8 is a graph comparing long cycle performance at 0.5C rate of the assembled full cells in example 1 and comparative example 1.
Fig. 9 is an SEM image of the negative electrode after the full cell assembled in example 1 was cycled at 0.5C magnification for 100 weeks.
FIG. 10 is a graph of the current density at 1mA/cm for a cell assembled in example 22The capacity is 1mAh/cm2SEM image of electrode after 100 weeks of lower cycle.
Fig. 11 is an SEM image of the negative electrode after the full cell assembled in example 2 was cycled at 0.5C magnification for 100 weeks.
Fig. 12 is an SEM image of the anode after the full cell assembled in comparative example 1 was cycled at 0.5C magnification for 100 weeks.
Figure 13 is a surface SEM image of the NGO @ Zn side deposited with an NGO overcoat as prepared in comparative example 2.
FIG. 14 is a graph showing the current density of 1mA/cm for a cell assembled in comparative example 22The capacity is 1mAh/cm2Cyclic performance graph of time.
Fig. 15 is an SEM image of the anode after the full cell assembled in comparative example 2 was cycled at 0.5C magnification for 100 weeks.
Detailed Description
The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification.
In the following examples:
the functionalized graphene material is prepared by the following method:
calcining graphene oxide at 600 ℃ for 1-5 h in an ammonia atmosphere, and obtaining nitrogen-doped graphene materials with different doping amounts by regulating and controlling the calcining time;
concentrated phosphoric acid (mass fraction 85% -86%) and graphene oxide are mixed according to a ratio of 1 mL: 200mg, calcining for 2 hours at 600 ℃ under the protection of argon atmosphere to obtain a phosphorus-doped graphene material with the doping amount of 1.5 wt%;
mixing graphene oxide and benzyl disulfide according to the mass ratio of 2:1, and calcining for 2 hours at 600 ℃ under the protection of argon atmosphere to obtain a sulfur-doped graphene material with the doping amount of 1.5 wt%;
graphene oxide material: purchased from Nanjing Xiancheng nanomaterial science and technology Co.
And (4) SEM characterization: the microscopic morphology of the sample was observed with a field emission scanning electron microscope (Hitachi SU-7) at an accelerating voltage of 5.0 kV.
Assembling a CR 2032 battery: the negative electrode materials prepared in the examples or comparative examples were used as positive and negative electrodes, glass fiber was used as a separator, and the solute of the electrolyte was 2M zinc sulfate (ZnSO)4) The solvent of the electrolyte is deionized water, and the electrolyte is assembled into a pair of batteries; the negative electrode material prepared in example or comparative example was used as a negative electrode, LiMn2O4As anode, the solute of electrolyte is 1M zinc sulfate (ZnSO)4) And 2M lithium sulfate (Li)2SO4) And the solvent of the electrolyte is deionized water, and the full cell is assembled. And (3) carrying out electrochemical performance test on the CR 2032 battery by using a Land system, and recording test data by using corresponding software.
Example 1
(1) Selecting an N-doped graphene material (the N doping amount is 1.5 wt%) as a functionalized graphene material, adding the functionalized graphene material into absolute ethyl alcohol, and uniformly mixing to prepare slurry with the concentration of 3 mg/mL;
(2) firstly, sequentially polishing the surface to be deposited of the zinc foil by using 2000-mesh and 4000-mesh abrasive paper, removing an oxide film on the surface of the zinc foil, and enabling the surface of the zinc foil to be smooth and flat; vertically immersing a zinc foil (namely the surface of the zinc foil of which the functionalized graphene protective layer is to be deposited is vertical to the bottom surface of a beaker) into a beaker filled with deionized water, dropwise adding the slurry prepared in the step (1) into the beaker at a constant speed of 0.5mL/s from one side of the beaker opposite to the surface of the zinc foil to be deposited and at the center of the width of the zinc foil, when the slurry is spread on the water surface and the slurry is spread on the surface of the zinc foil to be deposited, vertically and upwards pulling the zinc foil at a constant speed of 1mm/s, depositing the functionalized graphene protective layer on the surface of the zinc foil to be deposited, which is pulled out from the solution, and directly wiping off the zinc foil by using dust-free paper if the functionalized graphene is not locally deposited on the other surface of the zinc foil;
(3) and (3) vertically immersing the zinc foil deposited with the functionalized graphene protective layer obtained in the step (2) into a beaker filled with deionized water, repeating the vertical pulling operation of the step (2) for 3 times, repeatedly depositing the functionalized graphene protective layer on the functionalized graphene protective layer deposited on the surface of the zinc foil, and finally drying in a 65 ℃ oven to obtain the ultrathin interface modified zinc metal cathode material, which is abbreviated as NGO @ Zn.
From the photograph of fig. 1, it can be found that the NGO @ Zn prepared in this example macroscopically covers the zinc foil with the functionalized graphene protective layer (abbreviated as NGO protective layer) uniformly.
The micro-topography of the NGO @ Zn prepared in this example was characterized, and as can be seen from the surface SEM image in fig. 2, a large number of NGO wrinkles were present on the zinc foil surface, indicating that the NGO protective layer was successfully covered on the zinc foil surface; as can be seen from the cross-sectional SEM image in fig. 3, the NGO protective layer deposited on the zinc foil is 120nm thick.
The NGO @ Zn prepared in this example was assembled as a positive and negative electrode into CR 2032 pairs of batteries, and subjected to cycle performance testing. As can be seen from the test results of FIG. 4, the current density was 1mA/cm2And a capacity of 1mAh/cm2In the case of (3), the voltage curve is still flat after the battery is cycled for more than 1200h, the overpotential is only 17mV, the overpotential is small and has no obvious fluctuation, and the cycle performance of the battery is obviously better than that of the battery in comparative example 1.
The NGO @ Zn prepared in the example is used as a positive electrode and a negative electrode to assemble CR 2032 pairs of batteries, and the current density is 1mA/cm2And a capacity of 1mAh/cm2After the battery is cycled for 100 weeks, microscopic morphology observation is carried out on the NGO @ Zn negative electrode in the battery, and the NGO @ Zn negative electrode after the battery is cycled for 100 weeks is clear and flat in surface morphology and free of obvious zinc dendrite growth, as shown in FIG. 7. The NGO @ Zn anodes prepared in this example effectively inhibited the growth of zinc dendrites compared to the pure zinc foil anode surface after 100 weeks cycling of the cell in comparative example 1 (see figure 6 for details).
NGO @ Zn prepared in the example is used as a negative electrode, and LiMn2O4As a positive electrode, a CR 2032 full cell was assembled, and a long cycle performance test was performed at a rate of 0.5C (1C ═ 145 mAh/g). As can be seen from the test results of FIG. 8, the full battery using NGO @ Zn as the negative electrode shows excellent cycle stability, the specific discharge capacity after 300 cycles is 112mAh/g, and the capacity is maintainedThe rate is still 94%, which is much higher than the capacity retention rate after 300 weeks of full cell cycling in comparative example 1.
NGO @ Zn prepared in the example is used as a negative electrode, and LiMn2O4The positive electrode is assembled into a CR 2032 full cell, and after the full cell is cycled for 100 weeks at a multiplying power of 0.5C, the microscopic morphology of the NGO @ Zn negative electrode in the full cell is observed, so that the NGO @ Zn negative electrode after the full cell is cycled for 100 weeks is flat in surface and zinc is uniformly deposited, as shown in FIG. 9.
Example 2
On the basis of the embodiment 1, only the N-doped graphene material (N doping amount is 1.5 wt%) in the step (1) is replaced by the P-doped graphene material (P doping amount is 1.5 wt%), and other steps and conditions are not changed, so that the ultrathin interface modified zinc metal negative electrode material, which is abbreviated as PGO @ Zn, is obtained correspondingly.
Macroscopically, it can be seen that in the PGO @ Zn prepared in this embodiment, the functionalized graphene protective layer (abbreviated as PGO protective layer) uniformly covers the zinc foil.
The microscopic morphology of the PGO @ Zn prepared in the embodiment is characterized, and according to the characterization result, a large number of PGO wrinkles are found on the surface of the zinc foil, which indicates that the PGO protective layer successfully covers the surface of the zinc foil, and the thickness of the PGO protective layer deposited on the zinc foil is 116 nm.
PGO @ Zn prepared in the example was used as a positive and negative electrode to assemble a CR 2032 pair cell at a current density of 1mA/cm2And a capacity of 1mAh/cm2In the case of (2), the voltage curve of the pair of batteries is still flat after the batteries are cycled for more than 1200h, the overpotential is only 20mV, and the overpotential is small and has no obvious fluctuation.
PGO @ Zn prepared in the example was used as a positive and negative electrode to assemble a CR 2032 pair cell at a current density of 1mA/cm2And a capacity of 1mAh/cm2After the battery is cycled for 100 weeks, microscopic morphology observation is carried out on the PGO @ Zn negative electrode in the battery, and the PGO @ Zn negative electrode after the battery is cycled for 100 weeks is clear and flat in surface morphology and free of obvious zinc dendrite growth, as shown in FIG. 10.
PGO @ Zn prepared in the example was used as a negative electrode, and LiMn2O4As a positive electrode, assembled into a CR 2032 alloyThe battery was tested for long cycle performance at 0.5C rate. According to test results, the full battery taking PGO @ Zn as the cathode shows excellent cycling stability, the specific discharge capacity after 300 cycles is 102mAh/g, and the capacity retention rate is still 90%.
PGO @ Zn prepared in the example was used as a negative electrode, and LiMn2O4As the positive electrode, a CR 2032 full cell was assembled, and after cycling at a rate of 0.5C for 100 weeks, microscopic morphology of the PGO @ Zn negative electrode in the full cell was observed, and it was found that the PGO @ Zn negative electrode after cycling for 100 weeks had a flat surface and zinc was uniformly deposited, as shown in fig. 11.
Example 3
On the basis of the example 1, except that the N-doped graphene material (N doping amount is 1.5 wt%) in the step (1) is replaced by the S-doped graphene material (S doping amount is 1.5 wt%), and other steps and conditions are not changed, accordingly, the ultrathin interface modified zinc metal negative electrode material, which is abbreviated as SGO @ Zn, is obtained.
Macroscopically, it can be seen that in the SGO @ Zn prepared in this embodiment, a functionalized graphene protective layer (abbreviated as SGO protective layer) uniformly covers the zinc foil.
The microscopic morphology of the SGO @ Zn prepared in the embodiment is characterized, and according to the characterization result, a large number of SGO wrinkles are found on the surface of the zinc foil, which indicates that the SGO protective layer successfully covers the surface of the zinc foil, and the thickness of the SGO protective layer deposited on the zinc foil is 113 nm.
The SGO @ Zn prepared in the example is used as a positive electrode and a negative electrode to be assembled into a CR 2032 pair battery, and the current density is 1mA/cm2And a capacity of 1mAh/cm2In the case of (2), the voltage curve of the pair of batteries is still flat after the batteries are cycled for more than 1200h, the overpotential is only 20mV, and the overpotential is small and has no obvious fluctuation.
The SGO @ Zn prepared in the example is used as a positive electrode and a negative electrode to be assembled into a CR 2032 pair battery, and the current density is 1mA/cm2And a capacity of 1mAh/cm2After the battery is cycled for 100 weeks, microscopic morphology observation is carried out on the SGO @ Zn negative electrode in the battery, and the SGO @ Zn negative electrode after the battery is cycled for 100 weeks is clear and smooth in surface morphology and free of obvious zinc dendrite growth.
The SGO @ Zn prepared in the example is used as a negative electrode, and LiMn2O4As a positive electrode, a CR 2032 full cell was assembled, and a long cycle performance test was performed at a rate of 0.5C. According to test results, the full battery taking SGO @ Zn as the negative electrode shows excellent cycling stability, the specific discharge capacity after 300 cycles is 96mAh/g, and the capacity retention rate is still 88%.
The SGO @ Zn prepared in the example is used as a negative electrode, and LiMn2O4And the anode is used as an anode and assembled into a CR 2032 full cell, and after the full cell is cycled for 100 weeks under the multiplying power of 0.5C, the microscopic morphology of the SGO @ Zn anode in the full cell is observed, so that the surface of the SGO @ Zn anode after the full cell is cycled for 100 weeks is flat, and zinc is uniformly deposited.
Example 4
(1) Selecting an N-doped graphene material (the N doping amount is 1.5 wt%) as a functionalized graphene material, adding the functionalized graphene material into absolute ethyl alcohol, and uniformly mixing to prepare slurry with the concentration of 1 mg/mL;
(2) firstly, sequentially polishing the surface to be deposited of the zinc foil by using 2000-mesh and 4000-mesh abrasive paper, removing an oxide film on the surface of the zinc foil, and enabling the surface of the zinc foil to be smooth and flat; vertically immersing a zinc foil (namely the surface of the zinc foil on which a functionalized graphene protective layer is to be deposited is vertical to the bottom surface of a beaker) into a beaker filled with deionized water, dropwise adding the slurry prepared in the step (1) into the beaker at a constant speed of 1mL/s from one side of the beaker opposite to the surface of the zinc foil to be deposited and at the center of the width of the zinc foil, vertically and upwards lifting the zinc foil at a constant speed of 2mm/s when the slurry is spread on the water surface and the slurry is spread on the surface of the zinc foil to be deposited, depositing the functionalized graphene protective layer on the surface of the zinc foil to be deposited, which is lifted from the solution, and directly wiping off the zinc foil by using dust-free paper if functionalized graphene is locally deposited on the other surface of the zinc foil which is not required to be deposited;
(3) and (3) vertically immersing the zinc foil deposited with the functionalized graphene protective layer obtained in the step (2) into a beaker filled with deionized water, repeating the vertical pulling operation of the step (2) for 3 times, repeatedly depositing the functionalized graphene protective layer on the functionalized graphene protective layer deposited on the surface of the zinc foil, and finally drying in a 65 ℃ oven to obtain the ultrathin interface modified zinc metal cathode material, which is abbreviated as NGO @ Zn.
Macroscopically, the NGO @ Zn prepared in this example had an NGO protective layer uniformly covering the zinc foil.
The micro-topography of the NGO @ Zn prepared in this example was characterized, and according to the characterization results, it was found that there were a large number of NGO wrinkles on the zinc foil surface, indicating that the NGO protective layer was successfully covered on the zinc foil surface, and that the NGO protective layer deposited on the zinc foil was 80nm thick.
NGO @ Zn prepared in the example is used as a positive electrode and a negative electrode to be assembled into a CR 2032 pair battery, and the current density is 1mA/cm2And a capacity of 1mAh/cm2In the case of (2), the voltage curve is still flat after the battery is cycled for more than 1200h, the overpotential is only 20mV, and the overpotential is small and has no obvious fluctuation.
The NGO @ Zn prepared in the example is used as a positive electrode and a negative electrode to assemble CR 2032 pairs of batteries, and the current density is 1mA/cm2And a capacity of 1mAh/cm2After the battery is cycled for 100 weeks, microscopic morphology observation is carried out on the NGO @ Zn negative electrode in the battery, and the NGO @ Zn negative electrode after the battery is cycled for 100 weeks is clear and smooth in surface morphology and free of obvious zinc dendrite growth.
NGO @ Zn prepared in the example is used as a negative electrode, and LiMn2O4As a positive electrode, a CR 2032 full cell was assembled, and a long cycle performance test was performed at a rate of 0.5C. According to test results, the full battery taking NGO @ Zn as the negative electrode shows excellent cycling stability, the specific discharge capacity after 300 cycles is 106mAh/g, and the capacity retention rate is still 89%.
NGO @ Zn prepared in the example is used as a negative electrode, and LiMn2O4And the anode is used as an anode and assembled into a CR 2032 full cell, and after the full cell is cycled for 100 weeks under the multiplying power of 0.5C, the microscopic morphology of the NGO @ Zn anode in the full cell is observed, so that the NGO @ Zn anode after the full cell is cycled for 100 weeks has a smooth surface and zinc is uniformly deposited.
Example 5
(1) Selecting an N-doped graphene material (the N doping amount is 1.5 wt%) as a functionalized graphene material, adding the functionalized graphene material into absolute ethyl alcohol, and uniformly mixing to prepare slurry with the concentration of 3 mg/mL;
(2) firstly, polishing the surface of the zinc foil to be deposited by using 2000-mesh sand paper, removing an oxide film on the surface of the zinc foil, and enabling the surface of the zinc foil to be smooth and flat; vertically immersing a zinc foil (namely the surface of the zinc foil on which a functionalized graphene protective layer is to be deposited is vertical to the bottom surface of a beaker) into a beaker filled with deionized water, dropwise adding the slurry prepared in the step (1) into the beaker at a constant speed of 1mL/s from one side of the beaker opposite to the surface of the zinc foil to be deposited and at the center of the width of the zinc foil, when the slurry is spread on the water surface and the slurry is spread on the surface of the zinc foil to be deposited, vertically and upwards lifting the zinc foil at a constant speed of 1mm/s, depositing a functionalized graphene protective layer on the surface of the zinc foil to be deposited, which is lifted from the solution, and directly wiping off the zinc foil by using dust-free paper if functionalized graphene is locally deposited on the other surface of the zinc foil which is not required to be deposited;
(3) and (3) vertically immersing the zinc foil deposited with the functionalized graphene protective layer obtained in the step (2) into a beaker filled with deionized water, repeating the vertical pulling operation of the step (2) for 6 times, repeatedly depositing the functionalized graphene protective layer on the functionalized graphene protective layer deposited on the surface of the zinc foil, and finally drying in a 65 ℃ oven to obtain the ultrathin interface modified zinc metal cathode material, which is abbreviated as NGO @ Zn.
Macroscopically, the NGO @ Zn prepared in this example had an NGO protective layer uniformly covering the zinc foil.
The micro-topography of the NGO @ Zn prepared in the embodiment is characterized, and a large amount of NGO folds are formed on the surface of the zinc foil, so that the NGO protective layer successfully covers the surface of the zinc foil; as can be seen from the cross-sectional SEM images, the NGO protective layer deposited on the zinc foil was 2 μm thick.
NGO @ Zn prepared in the example is used as a positive electrode and a negative electrode to be assembled into a CR 2032 pair battery, and the current density is 1mA/cm2And a capacity of 1mAh/cm2In the case of (2), the voltage curve is still flat after the battery is cycled for more than 400 hours, the overpotential is 42mV, and the overpotential is small and has no obvious fluctuation.
The NGO @ Zn prepared in the example is used as a positive electrode and a negative electrode to assemble CR 2032 pairs of batteries, and the current density is 1mA/cm2And a capacity of 1mAh/cm2After the battery is cycled for 100 weeks, microscopic morphology observation is carried out on the NGO @ Zn negative electrode in the battery, and the NGO @ Zn negative electrode after the battery is cycled for 100 weeks is clear and smooth in surface morphology and free of obvious zinc dendrite growth.
NGO @ Zn prepared in the example is used as a negative electrode, and LiMn2O4As a positive electrode, a CR 2032 full cell was assembled, and a long cycle performance test was performed at a rate of 0.5C. According to test results, the full battery taking NGO @ Zn as the negative electrode shows excellent cycling stability, the specific discharge capacity after 300 cycles is 92mAh/g, and the capacity retention rate is still 85%.
NGO @ Zn prepared in the example is used as a negative electrode, and LiMn2O4And the anode is used as an anode and assembled into a CR 2032 full cell, and after the full cell is cycled for 100 weeks under the multiplying power of 0.5C, the microscopic morphology of the NGO @ Zn anode in the full cell is observed, so that the NGO @ Zn anode after the full cell is cycled for 100 weeks has a smooth surface and zinc is uniformly deposited.
Example 6
(1) Selecting an N-doped graphene material (the N doping amount is 2.5 wt%) as a functionalized graphene material, adding the functionalized graphene material into absolute ethyl alcohol, and uniformly mixing to prepare slurry with the concentration of 4 mg/mL;
(2) firstly, polishing the surface of the zinc foil to be deposited by 3000 meshes of sand paper, removing an oxide film on the surface of the zinc foil, and making the surface of the zinc foil smooth and flat; vertically immersing a zinc foil (namely the surface of the zinc foil on which a functionalized graphene protective layer is to be deposited is vertical to the bottom surface of a beaker) into a beaker filled with deionized water, dropwise adding the slurry prepared in the step (1) into the beaker at a constant speed of 1mL/s from one side of the beaker opposite to the surface of the zinc foil to be deposited and at the center of the width of the zinc foil, when the slurry is spread on the water surface and the slurry is spread on the surface of the zinc foil to be deposited, vertically and upwards lifting the zinc foil at a constant speed of 1mm/s, depositing a functionalized graphene protective layer on the surface of the zinc foil to be deposited, which is lifted from the solution, and directly wiping off the zinc foil by using dust-free paper if functionalized graphene is locally deposited on the other surface of the zinc foil which is not required to be deposited;
(3) and (3) vertically immersing the zinc foil deposited with the functionalized graphene protective layer obtained in the step (2) into a beaker filled with deionized water, repeating the vertical pulling operation of the step (2) for 2 times, repeatedly depositing the functionalized graphene protective layer on the functionalized graphene protective layer deposited on the surface of the zinc foil, and finally drying in a 65 ℃ oven to obtain the ultrathin interface modified zinc metal cathode material, which is abbreviated as NGO @ Zn.
Macroscopically, the NGO @ Zn prepared in this example had an NGO protective layer uniformly covering the zinc foil.
The micro-topography of the NGO @ Zn prepared in this example was characterized, and according to the characterization results, it was found that there were a large number of NGO wrinkles on the zinc foil surface, indicating that the NGO protective layer was successfully covered on the zinc foil surface, and that the NGO protective layer deposited on the zinc foil was 180nm thick.
NGO @ Zn prepared in the example is used as a positive electrode and a negative electrode to be assembled into a CR 2032 pair battery, and the current density is 1mA/cm2And a capacity of 1mAh/cm2In the case of (2), the voltage curve is still flat after the battery is cycled for more than 800 hours, the overpotential is 32mV, and the overpotential is small and has no obvious fluctuation.
The NGO @ Zn prepared in the example is used as a positive electrode and a negative electrode to assemble CR 2032 pairs of batteries, and the current density is 1mA/cm2And a capacity of 1mAh/cm2After the battery is cycled for 100 weeks, microscopic morphology observation is carried out on the NGO @ Zn negative electrode in the battery, and the NGO @ Zn negative electrode after the battery is cycled for 100 weeks is clear and smooth in surface morphology and free of obvious zinc dendrite growth.
NGO @ Zn prepared in the example is used as a negative electrode, and LiMn2O4As a positive electrode, a CR 2032 full cell was assembled, and a long cycle performance test was performed at a rate of 0.5C. According to test results, the full battery taking NGO @ Zn as the negative electrode shows excellent cycling stability, the specific discharge capacity after 300 cycles is 97mAh/g, and the capacity retention rate is still 88%.
NGO @ Zn prepared in the example is used as a negative electrode, and LiMn2O4And the anode is used as an anode and assembled into a CR 2032 full cell, and after the full cell is cycled for 100 weeks under the multiplying power of 0.5C, the microscopic morphology of the NGO @ Zn anode in the full cell is observed, so that the NGO @ Zn anode after the full cell is cycled for 100 weeks has a smooth surface and zinc is uniformly deposited.
Comparative example 1
Pure zinc foil is selected as a positive electrode and a negative electrode to assemble a CR 2032 pair of batteries, and the current density is 1mA/cm2And a capacity of 1mAh/cm2In the case of (2), the potential fluctuation is large after the battery is cycled for 100 hours, the overpotential rapidly increases during the cycling, and the inside of the battery is short-circuited when the battery is cycled for about 190 hours, as shown in fig. 5.
Pure zinc foil is selected as a positive electrode and a negative electrode to assemble a CR 2032 pair of batteries, and the current density is 1mA/cm2And a capacity of 1mAh/cm2After the battery is cycled for 100 weeks, the microscopic morphology observation of the pure zinc foil negative electrode in the pair of batteries shows that the surface of the pure zinc foil negative electrode after the battery is cycled for 100 weeks presents obvious loose and porous flaky dendrites, as shown in fig. 6.
Pure zinc foil is selected as a negative electrode, LiMn2O4As a positive electrode, a CR 2032 full cell was assembled, and a long cycle performance test was performed at a rate of 0.5C. According to the test results, the specific discharge capacity of the full-cell taking the pure zinc foil as the negative electrode after 300 weeks of cycling is 91mAh/g, and the capacity retention rate is only 74%.
Pure zinc foil is selected as a negative electrode, LiMn2O4When the full-cell CR 2032 is assembled as the positive electrode and cycled at a rate of 0.5C for 100 weeks, the microscopic morphology of the pure zinc foil negative electrode in the full-cell is observed, and serious side reaction products appear on the surface of the pure zinc foil negative electrode after cycling for 100 weeks, as shown in fig. 12.
Comparative example 2
(1) Selecting an N-doped graphene material (the N doping amount is 1.5 wt%) as a functionalized graphene material, adding the functionalized graphene material into absolute ethyl alcohol, and uniformly mixing to prepare slurry with the concentration of 7 mg/mL;
(2) firstly, polishing the surface of the zinc foil to be deposited by using 2000-mesh sand paper, removing an oxide film on the surface of the zinc foil, and enabling the surface of the zinc foil to be smooth and flat; vertically immersing a zinc foil (namely the surface of the zinc foil of which the functionalized graphene protective layer is to be deposited is vertical to the bottom surface of a beaker) into a beaker filled with deionized water, dropwise adding the slurry prepared in the step (1) into the beaker at a constant speed of 0.5mL/s from one side of the beaker opposite to the surface of the zinc foil to be deposited and at the center of the width of the zinc foil, when the slurry is spread on the water surface and the slurry is spread on the surface of the zinc foil to be deposited, vertically and upwards pulling the zinc foil at a constant speed of 1mm/s, depositing the functionalized graphene protective layer on the surface of the zinc foil to be deposited, which is pulled out from the solution, and directly wiping off the zinc foil by using dust-free paper if the functionalized graphene is not locally deposited on the other surface of the zinc foil;
(3) and (3) vertically immersing the zinc foil deposited with the functionalized graphene protective layer obtained in the step (2) into a beaker filled with deionized water, repeating the vertical pulling operation in the step (2) for 5 times, repeatedly depositing the functionalized graphene protective layer on the functionalized graphene protective layer deposited on the surface of the zinc foil, and finally drying in a 65 ℃ oven to obtain the ultrathin interface modified zinc metal cathode material, which is abbreviated as NGO @ Zn.
The NGO @ Zn prepared in this comparative example macroscopically functionalized graphene protective layer (abbreviated as NGO protective layer) completely covered on the zinc foil.
The micro-morphology characterization of the NGO @ Zn prepared by the comparative example is carried out, and according to the characterization result, a large number of NGO folds are found on the surface of the zinc foil, but a large number of uneven holes are presented on the surface, and the thickness distribution of the NGO protective layer deposited on the zinc foil is uneven, and the maximum thickness reaches 5 μm, as shown in FIG. 13.
NGO @ Zn prepared in the comparative example is used as a positive electrode and a negative electrode to be assembled into a CR 2032 pair battery, and the current density is 1mA/cm2And a capacity of 1mAh/cm2In the case of (2), the overpotential exhibited strong fluctuation within the battery cycle 100h, as shown in fig. 14, illustrating the nucleation and deposition unevenness of metallic zinc.
NGO @ Zn prepared in the comparative example was used as a negative electrode, LiMn2O4As a positive electrode, a CR 2032 full cell was assembled, and a long cycle performance test was performed at a rate of 0.5C. According to the test result, the discharge specific capacity of the full battery taking NGO @ Zn as the negative electrode is 80mAh/g after 300 weeks of circulation, and the capacity retention rate is 82%.
NGO @ Zn prepared in the comparative example was used as a negative electrode, LiMn2O4As a positive electrode, a CR 2032 full cell was assembled, and after cycling at a rate of 0.5C for 100 weeks, the full cell was microscopically examined for the NGO @ Zn negative electrodeMorphology observation revealed that the NGO @ Zn negative electrode surface exhibited significant plate-like dendrite growth after 100 weeks of cycling, as shown in fig. 15.
Comparative example 3
(1) Selecting an N-doped graphene material (the N doping amount is 1.5 wt%) as a functionalized graphene material, adding the functionalized graphene material into absolute ethyl alcohol, and uniformly mixing to prepare slurry with the concentration of 0.2 mg/mL;
(2) firstly, polishing the surface of the zinc foil to be deposited by using 2000-mesh sand paper, removing an oxide film on the surface of the zinc foil, and enabling the surface of the zinc foil to be smooth and flat; vertically immersing a zinc foil (namely the surface of the zinc foil of which the functionalized graphene protective layer is to be deposited is vertical to the bottom surface of a beaker) into a beaker filled with deionized water, dropwise adding the slurry prepared in the step (1) into the beaker at a constant speed of 0.5mL/s from one side of the beaker opposite to the surface of the zinc foil to be deposited and at the center of the width of the zinc foil, when the slurry is spread on the water surface and the slurry is spread on the surface of the zinc foil to be deposited, vertically and upwards pulling the zinc foil at a constant speed of 5mm/s, depositing the functionalized graphene protective layer on the surface of the zinc foil to be deposited, which is pulled out from the solution, and directly wiping off the zinc foil by using dust-free paper if the functionalized graphene is not locally deposited on the other surface of the zinc foil;
(3) and (3) vertically immersing the zinc foil deposited with the functionalized graphene protective layer obtained in the step (2) into a beaker filled with deionized water, repeating the vertical pulling operation of the step (2) for 3 times, repeatedly depositing the functionalized graphene protective layer on the functionalized graphene protective layer deposited on the surface of the zinc foil, and finally drying in a 65 ℃ oven to obtain the ultrathin interface modified zinc metal cathode material, which is abbreviated as NGO @ Zn.
Macroscopically, in the NGO @ Zn prepared by the comparative example, the functionalized graphene protective layer cannot be completely and uniformly coated on the zinc foil.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. An ultrathin interface modified zinc metal negative electrode material is characterized in that: the negative electrode material is a zinc-containing metal material with a functionalized graphene protective layer deposited on one surface;
the thickness of the functionalized graphene protective layer is 20 nm-3 mu m, the functionalized graphene is graphene doped with N, P or S heteroatom, and the mass percentage of the doped heteroatom is 1% -3%.
2. The ultrathin interface modified zinc metal negative electrode material as claimed in claim 1, characterized in that: the zinc-containing metal material is zinc foil or zinc alloy foil.
3. The ultrathin interface modified zinc metal negative electrode material as claimed in claim 1, characterized in that: the thickness of the functionalized graphene protective layer is 50 nm-1 μm.
4. The ultrathin interface modified zinc metal negative electrode material as claimed in claim 1, characterized in that: the thickness of the functionalized graphene protective layer is 80 nm-200 nm.
5. A preparation method of the ultrathin interface modified zinc metal negative electrode material as claimed in any one of claims 1 to 4, characterized by comprising the following steps: the steps of the method are as follows,
(1) adding the functionalized graphene material into an alcohol solvent to prepare slurry with the concentration of 1 mg/mL-5 mg/mL;
(2) removing an oxide film on the surface to be deposited of the zinc-containing metal material, vertically immersing the zinc-containing metal material into a container containing water, dropwise adding the slurry prepared in the step (1) into the container at a speed of 0.01-2 mL/s from one side of the container opposite to the surface to be deposited of the zinc-containing metal material, vertically lifting the zinc-containing metal material upwards at a speed of 0.5-10 mm/s when the slurry is spread on the water surface and the slurry is spread to the surface to be deposited of the zinc-containing metal material, depositing a functional graphene protective layer on the surface to be deposited of the zinc-containing metal material lifted out of the solution, and directly wiping the functional graphene protective layer off if the other surface, which does not need to be deposited, of the zinc-containing metal material is partially deposited with the functional graphene;
(3) and (3) vertically immersing the metal-containing material deposited with the functionalized graphene protective layer obtained in the step (2) into a container filled with water, repeating the lifting operation in the step (2), repeatedly depositing the functionalized graphene protective layer on the functionalized graphene protective layer deposited on the surface of the metal-containing material until the required thickness is reached, and finally drying to obtain the cathode material.
6. The preparation method of the ultrathin interface modified zinc metal anode material as claimed in claim 5, characterized in that: the alcohol solvent is methanol, ethanol or ethylene glycol.
7. The preparation method of the ultrathin interface modified zinc metal anode material as claimed in claim 5, characterized in that: the functionalized graphene material is prepared by the following method:
calcining graphene oxide at 550-650 ℃ for 1-5 h in an ammonia atmosphere to obtain a nitrogen-doped graphene material;
the mass fraction of concentrated phosphoric acid and graphene oxide of 85-86% is as follows 1 mL: (100-300) mg, and calcining at 550-650 ℃ for 1-5 h under the protection of inert gas atmosphere to obtain a phosphorus-doped graphene material;
mixing graphene oxide and benzyl disulfide according to the mass ratio of 1-5: 1, and calcining for 1-5 h at the temperature of 550-650 ℃ under the protection of an inert gas atmosphere to obtain the sulfur-doped graphene material.
8. The preparation method of the ultrathin interface modified zinc metal anode material as claimed in claim 5, characterized in that: and (3) polishing the surface to be deposited of the zinc-containing metal material by using 1000-4000 meshes of sand paper.
9. The preparation method of the ultrathin interface modified zinc metal anode material as claimed in claim 5, characterized in that: the concentration of the serous fluid is 1 mg/mL-5 mg/mL, the dropping speed of the serous fluid is 0.2 mL/s-1 mL/s, and the pulling speed of the zinc-containing metal material is 1 mm/s-3 mm/s.
10. The application of the ultrathin interface modified zinc metal negative electrode material as claimed in any one of claims 1 to 4, characterized in that: when the negative electrode material is applied to a water-based zinc ion battery, one surface of the negative electrode material deposited with the functionalized graphene protective layer is in contact with an electrolyte.
CN202110956730.9A 2021-08-19 2021-08-19 Ultrathin interface modified zinc metal negative electrode material, and preparation and application thereof Pending CN113871620A (en)

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