CN115425223A - Method for inducing super-conformal horizontal zinc deposition by liquid metal - Google Patents

Method for inducing super-conformal horizontal zinc deposition by liquid metal Download PDF

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Publication number
CN115425223A
CN115425223A CN202211209509.8A CN202211209509A CN115425223A CN 115425223 A CN115425223 A CN 115425223A CN 202211209509 A CN202211209509 A CN 202211209509A CN 115425223 A CN115425223 A CN 115425223A
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China
Prior art keywords
zinc
liquid metal
horizontal
deposition
conformal
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CN202211209509.8A
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Chinese (zh)
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付磊
曾梦琪
邹娟
汪晨阳
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Wuhan University WHU
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Wuhan University WHU
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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A method of liquid metal induced super-conformal horizontal zinc deposition is disclosed. According to the method, super-conformal horizontal zinc deposition is induced by introducing liquid metal in-situ alloying, and the zinc and the liquid metal spontaneously generate an alloy epitaxial interface, so that a zinc metal cathode is comprehensively protected from generating zinc dendrites in the charge-discharge cycle process, and the problems of low cycle stability, easiness in short circuit and the like of a zinc metal battery are further solved. The application also provides a preparation method of the super-conformal horizontal zinc deposition, which comprises the following steps: the liquid metal is coated on the smooth titanium foil through a simple blade coating method, a certain volume of zinc is pre-deposited, and a horizontal epitaxial interface is generated through in-situ alloying, so that horizontal zinc deposition is realized. The method for inducing super-conformal horizontal zinc deposition by liquid metal can protect a zinc metal cathode from dendritic crystal growth without dead angles of 360 degrees, can withstand higher current density and still keep better circulation stability, and can be applied to the field of zinc metal batteries.

Description

Method for inducing super-conformal horizontal zinc deposition by liquid metal
Technical Field
The application relates to the technical field of energy storage batteries, in particular to a method for inducing super-conformal horizontal zinc deposition by liquid metal.
Background
The zinc metal battery has the advantages of high energy density, good safety performance, rich raw materials, environmental friendliness and the like, and is a powerful candidate for the next-generation energy storage battery.
In the related art, the zinc cathode faces a very serious dendrite growth problem, and the zinc dendrite can seriously damage the service life of the battery, even pierce a diaphragm, cause short circuit, explosion and the like of the battery, and cause a serious safety problem. Therefore, it is crucial to find a method for suppressing zinc dendrites from the source of their growth.
Disclosure of Invention
In view of the above, the present application provides a method for inducing super-conformal horizontal zinc deposition by liquid metal, which can effectively prevent dendrite growth.
It has been generally recognized that metallic zinc cathodes face very serious dendrite growth problems, and zinc dendrites can seriously impair the service life of the battery, even pierce the separator, cause short circuit, explosion, etc., of the battery, and cause serious safety problems. Therefore, it is crucial to find a method for suppressing zinc dendrites from the source of their growth.
Since the melting point of liquid metal is generally 300 ℃ or lower, the liquid metal has both liquid and metal characteristics. The liquid metal is easy to alloy with various metals to form alloy with rich functions and properties. Meanwhile, the liquid metal reacts with oxygen in the air to generate a self-limiting oxide layer on the surface of the liquid metal, so that the liquid metal is endowed with good deformability, certain mechanical strength and adjustable surface tension. Meanwhile, the liquid metal has strong affinity with zinc, and the inventor unexpectedly finds that the liquid metal can be used in a zinc metal battery to effectively induce the deposition behavior of Zn.
The present application is based on the alloying reaction of liquid metal with zinc, introducing the liquid metal into a zinc metal battery. With the electrochemical deposition of zinc, the zinc will undergo an in-situ alloying reaction with the liquid metal to produce an alloy that exposes a particular crystal plane. The alloy has the same crystal symmetry as metal zinc in hexagonal close packing, and the exposed specific crystal face of the alloy has good lattice matching with the (002) crystal face of zinc, so that zinc can be induced to deposit along the (002) crystal face to obtain horizontally arranged zinc. In addition, because the liquid metal has good deformability, the obtained in-situ alloy, the titanium foil and the newly deposited zinc can be attached in a super-conformal manner, and 360-degree dead corners can be avoided to protect the zinc metal cathode from dendritic crystal growth.
In a first aspect, the present application provides a method for liquid metal induced super-conformal horizontal zinc deposition, comprising the steps of:
1) Fully oxidizing the liquid metal;
2) Attaching the liquid metal obtained in the step 1) to a template;
3) Coating the surface of the liquid metal in the step 2) with an insulating layer;
4) Assembling the material obtained in the step 3) and a zinc sheet into a symmetrical battery;
5) Applying current to the symmetrical battery obtained in the step 4) to enable the liquid metal surface to deposit zinc in situ.
Liquid metal as used herein generally refers to low melting point metals having a melting point below 200 c, which undergo a phase change to a liquid state when heated to a temperature at which the melting point is reached. The liquid metal is easily oxidized by oxygen in the air, and the fluidity of the liquid metal can be reduced by fully oxidizing the liquid metal at the melting point of the liquid metal through stirring, so that the stability of the liquid metal in the battery is maintained. There are studies showing that: the liquid metal is easily alloyed with other metals in the electrolyte, and based on this, the liquid metal is introduced into a zinc metal battery, and a horizontally epitaxial interface is obtained by in-situ alloying with zinc metal, thereby inducing horizontal deposition of zinc. Meanwhile, due to the excellent deformability of the liquid metal, an alloying epitaxial interface can be attached to the current collector and the newly deposited zinc in a super-conformal manner, so that 360-degree dead-angle-free protection of the zinc metal cathode is realized, and dendritic crystal growth is better prevented.
The liquid metal is selected from an alloy obtained by combining any one or more of gallium, indium, tin, cesium, rubidium, cadmium, bismuth and lead, and preferably gallium, indium, tin and corresponding alloys.
The pasty liquid metal can be obtained by stirring the liquid metal in the step 1) of the method, and the stirring time is 5-12 hours, preferably 8 hours.
The thickness of the liquid metal in step 2) of the present application is 5 to 15 μm, and the blade coating is performed using a four-corner preparation machine, preferably 10 μm.
The isolation layer in step 3) of the present application can be a conductive and zinc-phobic material for preventing the liquid metal from flowing in the battery and improving the survival rate of the battery, and includes any one of materials such as a single-walled carbon nanotube film, a double-walled carbon nanotube film, a graphene film, and the like, and is preferably a single-walled carbon nanotube film.
The disc size in step 4) of the present application is 10mm, 12mm, 14mm or 16mm, preferably 10mm or 12mm.
The current density of the in-situ deposited zinc in the step 5) of the application is 0.1mA cm –2 、0.2mA cm –2 、0.5mA cm –2 、1mA cm –2 Or 2mA cm –2 Preferably 0.5mA cm –2 (ii) a The capacity is 1mAh cm –2 、2mAh cm –2 、3mAh cm –2 、4mAh cm –2 、5mAh cm –2 、6mAh cm –2 、7mAh cm –2 、8mAh cm –2 、9mAh cm –2 Or 10mAh cm –2 Preferably 5mAh cm –2 。
According to the method, the metal zinc cathode is obtained by pre-depositing zinc on the liquid metal, and a horizontal alloy epitaxial template is generated by in-situ alloying of zinc and the liquid metal in the process, so that the subsequently deposited zinc presents a horizontal appearance. Meanwhile, the zinc metal cathode integrates the liquid advantage of liquid metal, and can be conformally attached to a current collector and continuously deposited zinc.
Compared with the prior art, the method has the following advantages and beneficial effects:
1. the application provides a method for tailoring a zinc metal battery, and an epitaxial interface capable of enabling zinc to grow horizontally is obtained through spontaneous in-situ alloying of liquid metal and zinc metal, so that zinc dendrites are fundamentally inhibited, and the stability of the battery is improved.
2. According to the method, the super-conformal horizontal zinc deposition is obtained by utilizing the intrinsic deformability of the liquid metal, the 360-degree dead-angle-free protection of the zinc metal cathode is realized, and the infinite potential in the flexible battery is shown.
3. The application provides a method for inducing super-conformal horizontal zinc deposition by liquid metal, which has controllable process conditions and simple process, can be prepared in a large area and is beneficial to promoting large-scale industrialization of zinc metal batteries.
Drawings
The technical solutions and other advantages of the present application will become apparent from the following detailed description of specific embodiments of the present application when taken in conjunction with the accompanying drawings.
FIG. 1 is a diagram of a titanium foil coated with a liquid metal prepared in example 1 of the present application;
FIG. 2 shows the pre-deposition of 3mAh cm for example 1 of the present application –2 And 5mAh cm –2 Scanning electron microscope top view after zinc;
FIG. 3 shows example 1 of the present application with 5mAh cm of pre-deposition –2 The scanning electron microscope side view and the element distribution diagram after zinc;
FIG. 4 shows the pre-deposition of 5mAh cm in example 1 of the present application –2 X-ray diffraction images after zinc;
FIG. 5 shows 5mAh cm deposited in example 1 of the present application –2 X-ray diffraction pattern after zinc and charge-discharge cycling for 30 cycles;
fig. 6 is a graph of the electrochemical performance of liquid metal induced super conformal horizontal zinc deposition in example 1 of the present application and the electrochemical performance of a comparative example zinc anode without liquid metal modification.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It should be apparent that the described embodiments are only a few embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
1) Taking 10g of gallium-indium eutectic alloy, stirring for 8 hours to fully oxidize the gallium-indium alloy to obtain pasty gallium-indium oxide alloy;
2) Coating the pasty gallium indium oxide alloy prepared in the step 1) on a smooth titanium foil, and repeatedly blade-coating the pasty gallium indium oxide alloy with a specification of 10 mu m by using a four-corner preparation device to obtain a uniform and flat gallium indium alloy film;
3) Covering the liquid metal in the step 2) with a single-walled carbon nanotube film to prevent the liquid metal from flowing;
4) Punching the material obtained in the step 3) into a wafer with the diameter of 10cm and assembling a symmetrical battery with a zinc sheet with the diameter of 12 cm;
5) 0.5mA cm in the cell assembled in step 4) –2 Current density in-situ deposition of 5mAh cm –2 To the liquid metal, obtaining a zn @ lm negative electrode with super conformal horizontal zinc deposition.
Example 2
1) Taking 10g of pure gallium, stirring for 8 hours at 40 ℃ to fully oxidize the gallium to obtain pasty gallium oxide;
2) Smearing the pasty gallium oxide prepared in the step 1) on a smooth titanium foil, and repeatedly scraping and coating the pasty gallium oxide with a specification of 10 mu m of a four-corner preparation device to obtain a uniform and flat gallium oxide film;
3) Covering the liquid metal in the step 2) with a single-walled carbon nanotube film;
4) Punching the material obtained in the step 3) into a wafer with the diameter of 10cm and assembling a symmetrical battery with a zinc sheet with the diameter of 12 cm;
5) 1mA cm in the cell assembled in step 4) –2 Current density in-situ deposition of 10mAh cm –2 To the liquid metal to obtain a cathode with super conformal horizontal zinc deposition.
Comparative example
1) Punching a smooth titanium foil into a wafer with the diameter of 10cm and assembling a symmetrical battery with a zinc sheet with the diameter of 12 cm;
2) 0.5mA cm in the cell assembled in step 1) –2 Current density in-situ deposition of 5mAh cm –2 The zinc can not be deposited on the titanium foil, and a negative electrode with zinc deposited at a super-common level can not be obtained, and the zinc can have a serious dendritic crystal growth phenomenon.
The relevant characterization and test data for example 1 are as follows:
FIG. 1 is a diagram showing the prepared liquid metal coated on a titanium foil. It can be seen from the figure that the liquid metal is very smooth and even when applied to the surface of the titanium foil, and it can be seen that the material can be prepared in a large area.
FIG. 2 is a graph of the current invention at 0.5mA cm for example 1 –2 At a current density of 3mAh cm –2 And 5mAh cm –2 Scanning electron microscope top view after zinc. As can be seen from the graph a, in the zinc pre-deposition process, when the deposition amount of zinc reaches 3mAh cm –2 The hexagonal horizontal zinc will exhibit a gradual splicing process. When 5mAh cm is pre-deposited –2 After the zinc is added, the hexagonal zinc is spliced to form a flat and compact plane. The surface appearance of the electrode is hexagonal layer by layer and is perfectly spliced, and the smooth and compact zinc deposition fundamentally inhibits the formation of dendrite and improves the cycle stability of the battery.
FIG. 3 shows example 1 of the present invention with 5mAh cm of pre-deposition –2 Scanning electron microscope side view of zinc. As can be seen, there is no clear line of demarcation between the alloy template and the freshly deposited zinc, and a conformal fit is present. The 360-degree dead angle-free protection of the cathode is realized.
FIG. 4 shows example 1 of the present invention with 5mAh cm of pre-deposition –2 X-ray diffraction pattern after zinc. According to the hexagonal close-packed structure of zinc and the characteristics of zinc deposition, the (002) crystal plane of zinc corresponds to the horizontal deposition of zinc, while the (001) and (101) crystal planes correspond to the vertical deposition of zinc, which causes the formation of zinc dendrites. As can be seen from the figure, the ratio of the diffraction peak of the (002) crystal plane to the diffraction peaks of the (001) and (101) crystal planes was increased by 24 times as compared with the electrode not modified with the liquid metal, and the liquid metal-modified electrode had almost only the (002) peak of zinc, which showed that zinc was deposited along the (002) crystal plane level, further demonstrating that zinc dendrite was fundamentally suppressed using the liquid metal-modified electrode.
FIG. 5 shows the deposition of 5mAh cm for example 1 of the present invention –2 Zinc at 1mA cm –2 Current density of (1 mAh cm) –2 X-ray diffraction pattern after 30 cycles of charge and discharge cycles.As can be seen from the figure, XRD still shows the same trend as fig. 4 even after 30 cycles of charge-discharge cycle, further demonstrating the protective effect of liquid metal on zinc negative electrode.
FIG. 6 shows example 1 of the present invention in which the liquid metal induces super-conformal horizontal zinc deposition at 1mA cm –2 Current density of (2) and 1mAh cm –2 A capacity of (c) is obtained. As can be seen from the figure, after the symmetrical battery is assembled with the zinc sheet, the negative electrode modified by the liquid metal can stably circulate for 360h. The voltage of the unmodified Zn cathode in the comparative example is greatly unstable after 30 hours; meanwhile, a voltage-time curve also shows that the overpotential of the battery modified by the liquid metal is lower and the polarization is smaller. The results prove that the method for inducing super-conformal horizontal zinc deposition by liquid metal can fundamentally inhibit the generation of zinc dendrites, improve the long-cycle stability of the battery and play a role in protecting zinc electrodes.
The above description is only for the preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present application should be covered within the scope of the present application.

Claims (8)

1. A method of liquid metal induced super conformal horizontal zinc deposition comprising the steps of:
1) Fully oxidizing the liquid metal;
2) Attaching the liquid metal obtained in the step 1) to a template;
3) Coating the surface of the liquid metal in the step 2) with an insulating layer;
4) Assembling the material obtained in the step 3) and a zinc sheet into a symmetrical battery;
5) Applying current to the symmetrical battery obtained in the step 4) to enable the liquid metal surface to deposit zinc in situ.
2. The method of claim 1, wherein the liquid metal is selected from the group consisting of gallium, indium, tin, cesium, rubidium, cadmium, bismuth, and lead.
3. The method according to claim 1, wherein stirring is applied during the oxidation in step 1), and the stirring time is 5-12 h.
4. The method of claim 1, wherein the thickness of the liquid metal in step 2) is 5 to 15 μm.
5. The method according to claim 1, wherein the material of the insulating layer in step 3) comprises any one of a carbon single-walled nanotube film, a double-walled carbon nanotube film, a graphene film, and the like.
6. The method as claimed in claim 1, wherein the material in step 4) is in the form of a disc having a diameter of 10mm, 12mm, 14mm or 16 mm.
7. The method as claimed in claim 1, wherein the current density of the in-situ deposited zinc in the step 5) is 0.5mA cm –2 (ii) a The capacity is 1mAh cm –2 、2mAh cm –2 、3mAh cm –2 、4mAh cm –2 、5mAh cm –2 、6mAh cm –2 、7mAh cm –2 、8mAh cm –2 、9mAh cm –2 Or 10mAh cm –2 。
8. A negative electrode material for a zinc metal battery, characterized by having a zinc deposition layer obtained by the method according to claim 1.
CN202211209509.8A 2022-09-30 2022-09-30 Method for inducing super-conformal horizontal zinc deposition by liquid metal Pending CN115425223A (en)

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Application Number Priority Date Filing Date Title
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