CN118039777B - Preparation method of heterogeneous zinc-indium alloy negative electrode - Google Patents
Preparation method of heterogeneous zinc-indium alloy negative electrode Download PDFInfo
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- CN118039777B CN118039777B CN202410444957.9A CN202410444957A CN118039777B CN 118039777 B CN118039777 B CN 118039777B CN 202410444957 A CN202410444957 A CN 202410444957A CN 118039777 B CN118039777 B CN 118039777B
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- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910000846 In alloy Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 74
- 239000011701 zinc Substances 0.000 claims abstract description 74
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 229910052738 indium Inorganic materials 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 230000005496 eutectics Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 239000006023 eutectic alloy Substances 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 12
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- 238000007086 side reaction Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 208000032953 Device battery issue Diseases 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0483—Processes of manufacture in general by methods including the handling of a melt
- H01M4/0488—Alloying
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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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of a heterogeneous zinc-indium alloy negative electrode. According to the invention, the heat treatment process is adopted to enable indium to be segregated at the metal zinc crystal boundary, so that simple preparation of the zinc-indium alloy is realized. In this alloy structure, indium is uniformly concentrated at zinc metal grain boundaries, and zinc has a single (002) texture. The preparation method has the advantages of simple process, low cost and large-scale production. The heterogeneous zinc-indium alloy prepared by the invention is used as a negative electrode of a water-based zinc battery and has excellent cycling stability.
Description
Technical Field
The invention relates to a preparation method of a heterogeneous zinc-indium alloy negative electrode, in particular to a preparation method of a zinc-indium alloy negative electrode, wherein metal indium is enriched at a zinc metal grain boundary, and zinc has a single (002) texture.
Background
The water-based Zinc Metal Battery (ZMBs) is considered as a powerful candidate for a large-scale energy storage technology because of the high theoretical capacity (820 mAh/g,5855 mAh/cm 3) and rich reserve of the used metal zinc negative electrode, and the high ionic conductivity, incombustibility, environmental friendliness and low price of the water-based electrolyte. Despite the above advantages, zinc metal used as a negative electrode may undergo side reactions such as hydrogen evolution and corrosion in an aqueous electrolyte, and irregular zinc deposition may generate dendrites during circulation to cause battery failure, severely impeding the practical application of ZMBs. Therefore, inhibition of side reactions and realization of uniform deposition of zinc are important for development and practical application of aqueous zinc batteries.
The current strategies for improving the performance of the zinc metal negative electrode mainly comprise structural design, crystal face regulation and control, interface modification, electrolyte regulation and control and the like. Commercial zinc foil consists of a large number of grains, there are a large number of grain boundaries and multiple textures coexist. And intergranular corrosion is very easy to occur at the grain boundary position, thereby aggravating side reaction and zinc dendrite growth and accelerating battery failure. In the prior art, it has been reported that the preparation of (002) texture zinc can effectively inhibit side reaction and induce zinc to epitaxially grow along (002) crystal face, thereby improving the cycle stability of zinc cathode. For example, by using single crystal (002) textured zinc as the zinc metal negative electrode, the single crystal zinc preparation process is complicated and extremely costly. For example, a strong (002) textured zinc anode is prepared by electrochemical deposition, annealing treatment, and rolling method, but it is difficult to obtain a single (002) textured zinc anode, and grain boundaries cannot be protected to reduce the influence of grain boundaries. The prior art reports that zinc grain boundaries can be partially occupied by preparing zinc-titanium alloys, the influence of the grain boundaries is reduced to a certain extent, but the non (002) texture cannot induce zinc epitaxial deposition. Thus, constructing a zinc anode with a single (002) texture and with the grain boundaries fully occupied is critical to improving the stability of the zinc anode.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a heterogeneous zinc-indium alloy negative electrode. The invention adopts a simple heat treatment process, and prepares the heterogeneous zinc-indium alloy anode with metal indium enriched at zinc metal grain boundary and zinc having single (002) texture by regulating and controlling the heat treatment temperature and the zinc-indium mass ratio. The preparation method has the advantages of simple process, low cost and large-scale production. The heterogeneous zinc-indium alloy anode prepared by the method is used as a water-based zinc-metal battery anode, and has extremely strong corrosion resistance and excellent cycling stability.
The preparation method of the heterogeneous zinc-indium alloy negative electrode is realized by the following technical scheme.
The invention provides a preparation method of a heterogeneous zinc-indium alloy negative electrode, which comprises the following steps: putting zinc and indium metal sheets into a reaction zone of a high-temperature furnace, and carrying out constant-temperature treatment on the zinc and indium metal sheets under the atmosphere of protective gas; after cooling, obtaining a heterogeneous zinc-indium alloy metal sheet with metal indium enriched at zinc metal grain boundaries and zinc having a single (002) texture; wherein the constant temperature treatment temperature is higher than the melting point temperature of zinc; the constant temperature treatment time is 1-30 minutes; the mass ratio of the zinc to the indium metal sheet is 96.5 to 97.7 percent, 2.3 to 3.5 percent; the cooling step comprises the following steps: and cooling the zinc and indium metal sheets after constant temperature treatment to ensure that the temperature is reduced to below the eutectic temperature (143.5 ℃) of zinc and indium after 2-3 hours.
As a preferred embodiment of the present invention, the temperature raising process is to heat the sample to the target temperature within 1 to 5 minutes.
As a preferred embodiment of the present invention, the constant temperature treatment temperature is 450-500 ℃.
As a preferred embodiment of the present invention, the constant temperature treatment time is 10 to 15 minutes.
As a preferable scheme of the invention, the mass ratio of the zinc metal sheet to the indium metal sheet is 97% -97.7%, namely 2.3% -3%; it is further preferable that the mass ratio of the zinc and indium metal sheets is 97.4% -97.7% and 2.3% -2.6%.
As a preferable scheme of the invention, the zinc and indium metal sheets are pretreated before constant temperature treatment; the pretreatment comprises ultrasonic cleaning of zinc sheet and indium sheet with ethanol or acetone, and oven drying.
As a preferable scheme of the invention, the heterogeneous zinc-indium alloy cathode obtained after cooling is subjected to polishing treatment, and the electrolytic polishing time is 5-30 minutes.
As a preferable mode of the present invention, the shielding gas is any one of argon, nitrogen, a mixture of hydrogen and argon, and a mixture of hydrogen and nitrogen.
As a preferred embodiment of the invention, the zinc metal sheet is preferably a high purity zinc foil having a purity of > 99.9%. The indium metal sheet is preferably indium foil with a purity of > 99.9%.
The heterogeneous zinc-indium alloy cathode prepared by the method is characterized in that the zinc-indium alloy is eutectic alloy, the solidified metal indium is enriched at zinc metal grain boundaries, and zinc has a single (002) texture.
The heterogeneous zinc-indium alloy anode prepared by the method is used for the anode of a water-based zinc metal battery, and has excellent cycle stability.
The preparation method of the heterogeneous zinc-indium alloy negative electrode provided by the invention has the following beneficial effects:
(1) The invention adopts a simple one-step heat treatment method, and realizes the rapid preparation of the heterogeneous zinc-indium alloy cathode by strictly regulating the mass ratio of zinc and indium, the heat treatment temperature, the heat treatment time and the cooling rate, and the cooling process in the invention needs slow cooling (namely, cooling to the eutectic temperature (143.5 ℃) of zinc and indium for 2-3 hours) so as to realize the full and uniform segregation of indium in zinc. The prepared heterogeneous zinc-indium alloy cathode has the characteristic that indium metal is segregated (enriched) at zinc crystal boundary, and zinc presents a single (002) texture.
(2) According to the zinc-indium alloy cathode, indium is segregated at the zinc crystal boundary, so that the interface of the zinc cathode can be stabilized, and the occurrence of intergranular corrosion and intergranular side reaction is reduced.
(3) The zinc-indium alloy cathode obtained by the invention has single (002) texture, so that zinc ions can be effectively induced to be deposited along the epitaxy of the (002) crystal face, dendrite growth and surface side reaction are inhibited, and the reversibility of the cathode is further improved.
(4) The zinc-indium alloy prepared by the invention is used as the negative electrode of a water-based zinc metal battery, has excellent cycle stability, and can be cycled for more than 4800 hours under the test conditions of 1 mA/cm 2 and 1 mAh/cm 2.
(5) Compared with the prior art, the invention has simple process and low cost, and can realize large-scale production.
Drawings
FIG. 1 is a digital photograph; in fig. 1a is the original zinc foil; in fig. 1b is a zinc indium alloy.
FIG. 2 is a diagram of the elemental distribution of the energy spectrum of a zinc-indium alloy scanning electron microscope; fig. 2a shows a zinc element distribution diagram; in fig. 2b is an indium element distribution diagram.
FIG. 3 is an X-ray diffraction pattern of the zinc-indium alloy prepared by the present invention.
Fig. 4 is a scanning electron microscope image of zinc epitaxial deposition on the surface of a zinc-indium alloy.
Detailed Description
The technical scheme of the invention is further described by combining the embodiments. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
The following are specific examples:
Example 1: the preparation method of the zinc-indium alloy negative electrode provided by the embodiment comprises the following steps:
(1) Ultrasonically cleaning high-purity zinc foil (99.99%) and high-purity indium foil (99.99%) with ethanol and acetone, and drying at room temperature;
(2) Cutting zinc foil (a in figure 1) and indium foil with proper sizes, wherein the mass ratio of the zinc foil to the indium foil is 97.4 percent (2.6 percent), and uniformly cutting the indium foil and then dispersing the zinc foil on the zinc foil;
(3) Placing zinc foil and indium foil into a reaction zone of a tube furnace, and carrying out constant temperature treatment on the zinc foil and the indium foil for 15 minutes at 450 ℃ under a protective atmosphere;
(4) The cooling rate is adjusted to cool the zinc indium after the constant temperature treatment to below the eutectic temperature (143.5 ℃) after 3 hours;
(5) After cooling to room temperature, the alloy was taken out to obtain a zinc-indium alloy (b in FIG. 1).
Wherein the heating rate of the constant temperature treatment is 20 ℃/min, and the protective atmosphere is argon; the cooling rate is 2 ℃/min; the indium metal in the alloy is uniformly segregated at zinc metal grain boundaries (fig. 2); and the zinc structure is single (002) crystal plane oriented (fig. 3).
The prepared zinc-indium alloy is used as an electrode after being polished and cleaned, and an electrochemical performance test is carried out on an assembled symmetrical battery, so that the zinc-indium alloy has excellent cycling stability, the surface of a zinc-indium alloy negative electrode presents uniform zinc epitaxial deposition morphology (figure 4), and the zinc-indium alloy can be cycled for more than 1000 hours under the test conditions of 5 mA/cm 2 and 5 mAh/cm 2.
Example 2: the preparation method of the zinc-indium alloy negative electrode provided by the embodiment comprises the following steps:
(1) Ultrasonically cleaning high-purity zinc foil (99.99%) and high-purity indium foil (99.99%) with ethanol and acetone, and drying at room temperature;
(2) Cutting zinc foil and indium foil with proper sizes, wherein the mass ratio of the zinc foil to the indium foil is 97.5 percent (2.5 percent), and uniformly cutting the indium foil and then dispersing the zinc foil on the zinc foil;
(3) Placing zinc foil and indium foil into a reaction zone of a tube furnace, and carrying out constant temperature treatment on zinc and indium for 15 minutes at 450 ℃ under a protective atmosphere;
(4) The cooling rate is adjusted to cool the zinc and indium after the constant temperature treatment to below the eutectic temperature (143.5 ℃) after 2 hours;
(5) And cooling to room temperature, and taking out to obtain the zinc-indium alloy.
Wherein the heating rate of the constant temperature treatment is 20 ℃/min, and the protective atmosphere is argon; the cooling rate is 2.5 ℃/min; the metal indium in the alloy is uniformly segregated at the zinc metal grain boundary; and the zinc structure is single (002) crystal plane orientation.
The prepared zinc-indium alloy is used as an electrode after being polished and cleaned, and the assembled symmetrical battery is subjected to electrochemical performance test, has excellent cycling stability, and can be cycled for more than 4800 hours under the test conditions of 1 mA/cm 2 and 1 mAh/cm 2. Under the test conditions of 10 mA/cm 2 and 10 mAh/cm 2, the cycle time can be still more than 800 hours.
Example 3: the preparation method of the zinc-indium alloy negative electrode provided by the embodiment comprises the following steps:
(1) Ultrasonically cleaning high-purity zinc foil (99.99%) and high-purity indium foil (99.99%) with ethanol and acetone, and drying at room temperature;
(2) Cutting zinc foil and indium foil with proper sizes, wherein the mass ratio is 97.6 percent to 2.4 percent, and uniformly cutting the indium foil and then dispersing the indium foil on the zinc foil;
(3) Zinc foil and indium foil are placed in a reaction zone of a tubular furnace, and zinc indium is subjected to constant temperature treatment for 15 minutes at 450 ℃ under a protective atmosphere;
(4) The cooling rate is adjusted to cool the zinc indium after the constant temperature treatment to below the eutectic temperature (143.5 ℃) after 3 hours;
(5) And cooling to room temperature, and taking out to obtain the zinc-indium alloy.
Wherein the heating rate of the heat treatment is 20 ℃/min, and the protective atmosphere is argon; the cooling rate is 2 ℃/min; the metal indium in the alloy is uniformly segregated at the zinc metal grain boundary; and the zinc structure is single (002) crystal plane orientation.
The prepared zinc-indium alloy is used as an electrode after being polished and cleaned, and the assembled symmetrical battery is subjected to electrochemical performance test, has excellent cycling stability, and can be cycled for more than 1500 hours under the test conditions of 10 mA/cm 2 and 5 mAh/cm 2.
Example 4: the preparation method of the zinc-indium alloy negative electrode provided by the embodiment comprises the following steps:
(1) Ultrasonically cleaning high-purity zinc foil (99.99%) and high-purity indium foil (99.99%) with ethanol and acetone, and drying at room temperature;
(2) Cutting zinc foil and indium foil with proper sizes, wherein the mass ratio is 97.7 percent to 2.3 percent, and uniformly cutting the indium foil and then dispersing the indium foil on the zinc foil;
(3) Putting zinc foil and indium foil into a reaction zone of a tube furnace, and carrying out constant temperature treatment on zinc indium at 460 ℃ for 12 minutes under a protective atmosphere;
(4) The cooling rate is adjusted to cool the zinc indium after heat treatment below the eutectic temperature (143.5 ℃) after 2 hours;
(5) And cooling to room temperature, and taking out to obtain the zinc-indium alloy.
Wherein the heating rate of the constant temperature treatment is 20 ℃/min, and the protective atmosphere is argon; the cooling rate is 2.5 ℃/min; the metal indium in the alloy is uniformly segregated at the zinc metal grain boundary; and the zinc structure is single (002) crystal plane orientation.
The prepared zinc-indium alloy is used as an electrode after being polished and cleaned, and an assembled symmetrical battery is subjected to electrochemical performance test, has excellent cycling stability, can be cycled for more than 2600 hours under the test conditions of 0.5 mA/cm 2 and 0.5 mAh/cm 2, and can be cycled for more than 3000 hours under the test conditions of 0.1 mA/cm 2 and 0.1 mAh/cm 2.
Comparative example 1:
ultrasonically cleaning high-purity zinc foil (99.99%) with ethanol and acetone, and drying at room temperature;
The zinc foil is sheared into proper size and then directly used as an electrode, the zinc metal symmetrical battery is assembled for electrochemical performance test, and the zinc metal symmetrical battery can be circulated for 130 hours only under the test conditions of 1 mA/cm 2 and 1 mAh/cm 2; under test conditions of 5 mA/cm 2 and 5 mAh/cm 2, circulation was only possible for 45 hours.
The foregoing is merely exemplary of embodiments of the present invention, which may be described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (8)
1. The preparation method of the heterogeneous zinc-indium alloy cathode is characterized by comprising the following steps of: putting zinc and indium metal sheets into a reaction zone of a high-temperature furnace, and carrying out constant-temperature treatment on the zinc and indium metal sheets under the atmosphere of protective gas; after cooling, obtaining a heterogeneous zinc-indium alloy anode with metal indium enriched at zinc metal grain boundary and zinc having single (002) texture; the constant temperature treatment temperature is higher than the melting point temperature of zinc; the constant temperature treatment time is 1-30 minutes; the mass ratio of the zinc metal sheet to the indium metal sheet is 96.5-97.7 percent, namely 2.3-3.5 percent; the cooling step includes: and (3) carrying out constant temperature treatment on the zinc and indium metal sheets, and then cooling to enable the temperature to be reduced to below the zinc-indium eutectic temperature after 2-3 hours.
2. The method for preparing a heterogeneous zinc-indium alloy anode according to claim 1, wherein the constant temperature treatment temperature is 450-500 ℃.
3. The method for preparing a heterogeneous zinc-indium alloy anode according to claim 1, wherein the constant temperature treatment time is 10-15 minutes.
4. The preparation method of the heterogeneous zinc-indium alloy anode according to claim 1, wherein the mass ratio of the zinc metal sheet to the indium metal sheet is 97.4% -97.7%, and 2.3% -2.6%.
5. The method of claim 1, wherein the zinc-indium alloy is a eutectic alloy, the indium is concentrated at the zinc grain boundaries and the zinc has a single (002) texture.
6. The method for preparing a heterogeneous zinc-indium alloy anode according to claim 1, wherein the steps further comprise: and polishing the heterogeneous zinc-indium alloy cathode obtained after cooling, wherein the electrolytic polishing time is 5-30 minutes.
7. The method for preparing a heterogeneous zinc-indium alloy anode according to claim 1, wherein the zinc-indium metal sheet is pretreated before the constant temperature treatment; the pretreatment comprises ultrasonic cleaning of zinc sheet and indium sheet with ethanol or acetone, and oven drying.
8. The method for preparing a heterogeneous zinc-indium alloy anode according to claim 1, wherein the shielding gas is any one of argon, nitrogen, a mixture of hydrogen and argon, and a mixture of hydrogen and nitrogen.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06318456A (en) * | 1992-02-13 | 1994-11-15 | Sanyo Electric Co Ltd | Manufacture of non-amalgamated negative electrode zinc alloy powder for alkaline battery |
| CN113972351A (en) * | 2021-10-22 | 2022-01-25 | 中南大学 | Zinc alloy cathode and preparation method and application thereof |
| CN117476860A (en) * | 2023-12-27 | 2024-01-30 | 南京邮电大学 | Preparation method of large-grain ultra-strong (002) texture zinc metal anode |
| CN117673240A (en) * | 2022-08-30 | 2024-03-08 | 上海交通大学 | Preparation method and application of monocrystal metal zinc negative electrode |
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| US20230282816A1 (en) * | 2022-03-04 | 2023-09-07 | Battelle Memorial Institute | Indium zinc-based alloy anodes forming porous structure for aqueous zinc batteries |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06318456A (en) * | 1992-02-13 | 1994-11-15 | Sanyo Electric Co Ltd | Manufacture of non-amalgamated negative electrode zinc alloy powder for alkaline battery |
| CN113972351A (en) * | 2021-10-22 | 2022-01-25 | 中南大学 | Zinc alloy cathode and preparation method and application thereof |
| CN117673240A (en) * | 2022-08-30 | 2024-03-08 | 上海交通大学 | Preparation method and application of monocrystal metal zinc negative electrode |
| CN117476860A (en) * | 2023-12-27 | 2024-01-30 | 南京邮电大学 | Preparation method of large-grain ultra-strong (002) texture zinc metal anode |
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