CN113013418A - Alloy framework supported zinc metal cathode and preparation method and application thereof - Google Patents
Alloy framework supported zinc metal cathode and preparation method and application thereof Download PDFInfo
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- CN113013418A CN113013418A CN202110450104.2A CN202110450104A CN113013418A CN 113013418 A CN113013418 A CN 113013418A CN 202110450104 A CN202110450104 A CN 202110450104A CN 113013418 A CN113013418 A CN 113013418A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000011701 zinc Substances 0.000 title claims abstract description 89
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 83
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 50
- 239000000956 alloy Substances 0.000 title claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 24
- 230000008021 deposition Effects 0.000 claims abstract description 22
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 208000028659 discharge Diseases 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 7
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000005275 alloying Methods 0.000 claims description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- -1 silver ions Chemical class 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 239000010963 304 stainless steel Substances 0.000 description 1
- 229910016374 CuSO45H2O Inorganic materials 0.000 description 1
- 229910002535 CuZn Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides an alloy framework supported zinc metal negative electrode and a preparation method and application thereof, wherein the zinc metal negative electrode comprises a three-dimensional current collector substrate, a zinc-based alloy layer and a zinc composite layer, wherein the zinc-based alloy layer and the zinc composite layer are coated on the surface of the three-dimensional current collector substrate, and the method comprises the following steps: step 1: pretreating the three-dimensional current collector substrate; step 2: preparing a Zn mixed solution as an electrolyte; and step 3: taking the three-dimensional current collector as a working electrode, and depositing the zinc sheet on the working electrode to obtain a modified three-dimensional current collector; and 4, step 4: and compounding the modified three-dimensional current collector with zinc to obtain the alloy framework supported zinc metal cathode. According to the invention, the three-dimensional current collector substrate and the alloy layer are effectively fused, the dissolution/deposition behavior of zinc ions in the battery is regulated, and the zinc-ion composite cathode is applied to the water-system zinc ion battery, so that zinc deposition can be uniformly induced, dendritic crystal generation is inhibited, higher reversibility of zinc deposition removal is maintained, and the stability and the cyclicity of the composite zinc metal cathode are improved.
Description
Technical Field
The invention relates to the technical field of water-based zinc ion batteries, in particular to an alloy framework supported zinc metal cathode and a preparation method and application thereof.
Background
With the aggravation of global energy crisis and the worsening of environment, the development of efficient energy storage systems is imperative. Lithium ion batteries are widely used in electronic devices such as mobile phones and computers due to their excellent electrochemical properties, but are also limited by the scarcity of metal lithium and the safety problem of organic electrolytes. Aqueous zinc ion batteries have received increasing attention due to their simple preparation, low cost, high mass and volume capacity, and rapid charge and discharge, and have become potential substitutes for lithium ion batteries. The metal zinc has the advantages of high conductivity, safety, environmental protection, low equilibrium potential (-0.76Vvs standard hydrogen electrode), high theoretical specific capacity (820mAh/g) and the like, and is always the most ideal negative electrode candidate in the water-based energy storage device.
However, the direct use of zinc as a negative electrode material also has the problem of zinc dendrite in the charging and discharging process, which seriously affects the cycle life of the zinc ion battery, and at present, there are three main solutions to this problem: zinc negative electrode surface modification, electrolyte modification and current collector modification. The current collector is the first choice for researchers because of its chemical inertness and good conductivity, and the three-dimensional current collector can reduce the actual current density and is an effective way to reduce the formation of dendrites. However, the traditional three-dimensional current collector has low affinity with zinc, and the existing affinity layer has the problems of complicated preparation process, difficult introduction of an organic layer and the like, so that designing and constructing the novel three-dimensional current collector modified zinc metal negative electrode has important scientific significance for further researching the growth behavior and inhibition method of zinc dendrites and developing high-performance zinc metal secondary batteries.
Disclosure of Invention
The invention provides an alloy framework supported zinc metal negative electrode and a preparation method and application thereof.
In order to achieve the purpose, the invention provides a zinc metal negative electrode supported by an alloy framework, which comprises a modified three-dimensional current collector and a zinc composite layer on the surface of the modified three-dimensional current collector, wherein the modified three-dimensional current collector comprises a three-dimensional current collector substrate and a zinc-based alloy layer coated on the surface of the three-dimensional current collector substrate.
Preferably, the three-dimensional current collector substrate is one of a stainless steel mesh, a nickel mesh, a titanium mesh, a copper mesh and a carbon mesh.
Preferably, the zinc-based alloy layer includes one or more of a zinc-copper alloy and a zinc-silver alloy.
Preferably, the zinc-copper alloy comprises Cu5Zn8And CuZn5The zinc-silver alloy is AgZn3。
More preferably, the zinc-copper alloy layer is CuZn5。
The invention also provides a preparation method of the alloy framework supported zinc metal cathode, which comprises the following steps:
step 1: pretreating the three-dimensional current collector substrate;
step 2: preparing a mixed solution containing zinc ions and alloy element ions as an electrolyte;
and step 3: performing deposition treatment on the three-dimensional current collector obtained in the step (1) as a working electrode and a zinc sheet counter electrode in the electrolyte obtained in the step (2) to obtain a modified three-dimensional current collector;
and 4, step 4: and (4) taking the modified three-dimensional current collector obtained in the step (3) as a positive electrode, assembling the positive electrode and a zinc foil into a battery, performing discharge treatment, and realizing the compounding of the modified three-dimensional current collector and zinc to obtain the alloy framework supported zinc metal negative electrode.
Preferably, the pretreatment specifically comprises: cutting the three-dimensional current collector substrate, then carrying out ultrasonic cleaning by using acid, water and alcohol in sequence, and drying.
Preferably, in the electrolyte, the ions of the alloying element include one of copper ions and silver ions; the molar concentration ratio of the alloy element ions to the zinc ions is 1: 25-100, more preferably, the molar concentration ratio of the alloy element ions to the zinc ions is 1:25, 1:50, 1:100, and further preferably: 1:100.
Preferably, in the step 3, the deposition current density is 1-9 mA cm-2The deposition time is 5 min; more preferably, the deposition current density is 1, 3, 5, 7, 9mA cm-2And further preferably 7mA cm-2。
Preferably, in step 4, the discharge treatment is: 0.2 to 0.4mA cm-2Constant current discharge for 12.5-25 h, more preferably 0.25mA cm-2And constant current discharging for 20 h.
The invention also provides application of the alloy framework supported zinc metal cathode, and a non-completely symmetrical battery is assembled by the alloy framework supported zinc metal cathode and a zinc foil.
The invention also provides application of the alloy framework supported zinc metal cathode, and the alloy framework supported zinc metal cathode is used as a cathode, namely CNT-MnO2Is used as a positive electrode to assemble the water-system zinc ion battery.
The scheme of the invention has the following beneficial effects:
the invention increases the interface contact area and reduces the local current density by utilizing the three-dimensional framework, directly constructs a metal alloy layer on the surface of the three-dimensional current collector by using the mixed electrolyte of copper salt and zinc salt in an electric field induced deposition mode and using different metal ions, reduces the zinc nucleation overpotential, has the function of inducing the zinc to be uniformly deposited, and can greatly improve the coulombic efficiency and the cycle life of the battery when being applied to the water system zinc ion battery.
Through effective fusion of current collector modification and alloying regulation, the deposition/dissolution behavior of zinc metal ions in the battery is regulated, the prepared copper-zinc alloy has good zinc affinity, the overpotential of zinc nucleation can be effectively reduced, and the deposition of zinc is uniformly induced, so that the nonuniform nucleation growth of zinc dendrites is inhibited, and the stability and the cyclicity of the composite zinc metal negative electrode are improved.
The alloy framework supported zinc metal cathode is applied to a non-completely symmetrical battery and is 0.5mA cm-20.25mAh cm-2The method can be stably cycled for more than 300h, has good reversibility and maintains a small overpotential.
The alloy framework supported zinc metal cathode is applied to an aqueous zinc ion battery, can stably circulate for 350 circles under the condition of 1A/g, still keeps the capacity above 120mAh/g, and has good circulation performance.
Drawings
FIG. 1 is a scanning electron micrograph of example 1 of the present invention.
FIG. 2 is a graph comparing coulombic efficiencies of example 1 of the present invention and comparative example 1.
FIG. 3 is a comparative in situ SEM image of example 1 of this experiment.
FIG. 4 is a scanning electron micrograph of example 2 of the present invention.
FIG. 5 is a graph comparing coulombic efficiencies of example 2 of the present invention with example 1 and comparative example 1.
FIG. 6 is a scanning electron micrograph of example 3 of the present invention.
FIG. 7 is a graph comparing coulombic efficiencies of example 3 of the present invention and comparative example 1.
FIG. 8 is a SEM image of example 4 of the present invention.
FIG. 9 is a graph comparing coulombic efficiencies of example 4 of the present invention and comparative example 1.
Fig. 10 is a comparative constant current charge and discharge diagram of example 5 of the present invention and comparative example 1.
Fig. 11 is a graph comparing the specific discharge capacity and efficiency of the full cells of example 5 of the present invention and comparative example 2.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Example 1
And (3) preparing and testing the modified three-dimensional current collector.
Selecting a 250-mesh 304 stainless steel net with the thickness of 200mm as a three-dimensional current collector substrate, firstly cutting the stainless steel net into a size of 2.5cm multiplied by 3cm, ensuring that the effective size of reaction during electrodeposition is 2cm multiplied by 3cm, sequentially carrying out ultrasonic cleaning on the cut stainless steel net for 10min by respectively using acid, deionized water and ethanol, removing surface impurities, and drying for later use. Cutting commercial zinc foil with the same size and thickness of 200mm, ultrasonic cleaning with deionized water and ethanol for 10min, and drying for later use.
23.0048g of ZnSO were weighed out next47H2O and 0.2g CuSO45H2O in H2In O, 2M ZnSO is prepared4And 20mM CuSO4The mixed solution of (2) is used as an electrolytic solution for electrodeposition.
Using an electrochemical workstation, adopting a two-electrode system, using a stainless steel net as a working electrode and a zinc foil as a counter electrode, using a 100mL electrolytic cell for electrodeposition under the condition of constant current, and setting the deposition current density to be 7mA cm-2And 5min, and after connection is finished, deposition is started. In the process, the surface color of the stainless steel mesh can be observed to gradually become dark, the pole piece is quickly taken down after the reaction is finished, the pole piece is placed in a culture dish, the surface redundant solution is washed by deionized water and ethanol, the pole piece is naturally dried at room temperature, and then the pole piece is cut into a round piece with the diameter of 14mm by a punch, namely the pole piece can be used as a modified three-dimensional current collector, which is marked as SS-CZ 7.
Wherein, FIG. 1 is the SS-CZ7 surface scanning electron microscope image obtained in example 1, it can be seen from the figure that a layer of uniform and dense nano-bulk material is deposited on the surface of the stainless steel mesh after electrodeposition, and the XRD result shows that the alloy is CuZn5。
The alloy skeleton is used as a current collector to be assembled with commercial zinc foil to form a half cell, and the half cell is SS-CZ7 used as a positive electrode and is arranged at 2mA cm-2，1mAh cm-2Under the condition, the coulombic efficiency and the cycling stability are tested, and as shown in figure 2, the coulombic efficiency which can be kept above 98% can be stably cycled for more than 450 circles.
Use of the originalThe behavior of zinc deposition during the first cycle was observed by optical microscopy, FIG. 3 is at 2mA cm-2Current density of 1mAh cm-2The original zinc is an optical electron microscope contrast image (all far away from the zinc sheet surface). As can be seen from the figure, zinc is uniformly deposited with CuZn5The existing stainless steel mesh fibers only thicken the fibers, so that the good effect of a three-dimensional current collector is maintained, and when the bare stainless steel mesh is deposited, zinc is deposited on the fibers and mostly deposited among gaps of the fibers, so that the subsequent zinc is difficult to remove, and the coulomb efficiency of the battery is reduced. Illustrating the CuZn prepared5Has better effect of inducing the uniform deposition of zinc.
Example 2
The deposition current density in example 1 was changed to 1, 3, 5, and 9mA cm respectively while keeping the other experimental conditions unchanged-2The time is 5min, the pole pieces are cut into round pieces with the diameter of 14mm by a punch after being dried, the round pieces are sequentially marked as SS-CZ1, SS-CZ3, SS-CZ5 and SS-CZ9, and a scanning electron microscope image is shown in figure 3, so that the appearance is changed from a nanometer ball shape to a nanometer block shape along with the increase of the density of the deposition current. The half cells were assembled with zinc foil, respectively, and FIG. 5 is a coulombic efficiency chart at 7mA cm-2The modified three-dimensional current collector obtained by the lower deposition, namely SS-CZ7, has optimal zinc deposition/extraction reversibility.
Example 3
The concentration of zinc sulfate in the electrolyte was reduced while keeping the other experimental conditions in example 1, and 40mL of 1M ZnSO was prepared4And 20mM CuSO4The mixed solution of (2) is used as an electrolytic solution for electrodeposition. The obtained modified three-dimensional current collector is shown in fig. 5, and the alloy layer is uniform in appearance; as shown in FIG. 7, the method can keep high coulombic efficiency and zinc deposition and extraction reversibility at 2mA cm-2，1mAh cm-2Can be stably circulated for 160 circles.
Example 4
The concentration of zinc sulfate in the electrolyte was reduced by keeping the other experimental conditions in example 1 constant, and 40mL of 0.5M ZnSO was prepared4And 20mM CuSO4As an electrode for electrodepositionAnd (4) hydrolyzing the liquid. The obtained modified three-dimensional current collector is shown in fig. 8, the alloy layer is uniform in morphology, and an XRD result shows that the modified three-dimensional current collector is Cu5Zn8With CuZn5The mixed alloy layer of (1). As shown in FIG. 9, at 2mA cm-2，1mAh cm-2Can stably circulate for 120 circles under the condition of (1).
Example 5
A preparation method and application of an alloy framework supported zinc metal cathode.
The half-cell was assembled from the pole piece SS-CZ7 obtained in example 1 and zinc foil, SS-CZ7 as the positive electrode, at 0.25mA cm-2Discharging for 20h under the current density of (1), namely depositing 5mA h of Zn as a zinc cathode, namely a three-dimensional zinc metal cathode supported by an alloy framework, assembling the three-dimensional zinc metal cathode and a zinc foil into a non-completely symmetrical battery at the current density of 0.5mA cm-20.25mAh cm-2Then, a non-completely symmetrical constant current charge and discharge test is carried out, and as shown in fig. 10, stable circulation can be carried out for more than 300 h. And a small overpotential is maintained.
Three-dimensional zinc cathode and CNT/MnO supported by the alloy framework2The positive pole piece is assembled into a full battery, and a charge-discharge test is carried out under the current density of 1A/g, as shown in figure 11, the zinc metal negative pole supported by the alloy framework can stably circulate for 350 circles, and the capacity is still kept above 120 mAh/g.
Comparative example 1
Cutting the unmodified stainless steel mesh into pieces with a certain size, cutting the pieces into round pieces with the diameter of 14mm by using a punch, respectively carrying out ultrasonic cleaning for 10min by using water and ethanol, and drying for later use, thus obtaining the pole piece used in the comparative example, which is recorded as SS. It was assembled with commercial zinc foil into a half cell and coulombic efficiency was tested. As shown in fig. 2, at 2mAcm-21mAh cm-2Under test conditions, coulombic efficiency is very low and unstable, and short circuit occurs quickly.
Comparative example 2
Assembling the unmodified stainless steel mesh and the zinc foil to form a half cell, wherein the unmodified stainless steel mesh is used as a positive electrode and the concentration of the positive electrode is 0.25mA cm-2Is discharged for 20 hours under the current density, namely Zn of 5mAh is deposited to be used as a zinc cathode, namely a three-dimensional zinc metal cathode, and then the zinc cathode is discharged at 0.5mA cm-20.25mAh cm-2Under the condition of non-completely symmetrical constant current charging and dischargingTesting, as shown in fig. 6, the cell has failed short circuit at 74 h.
The three-dimensional zinc cathode is connected with CNT/MnO2The positive pole piece is assembled into a full battery, and a charge-discharge test is carried out under the current density of 1A/g, as shown in figure 7, the capacity is rapidly attenuated, and after the cycle of 350 circles, the specific discharge capacity is less than 50 mAh/g.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The zinc metal negative electrode supported by the alloy framework is characterized by comprising a modified three-dimensional current collector and a zinc composite layer on the surface of the modified three-dimensional current collector, wherein the modified three-dimensional current collector comprises a three-dimensional current collector substrate and a zinc-based alloy layer coated on the surface of the three-dimensional current collector substrate.
2. The alloy skeleton-supported zinc metal negative electrode of claim 1, wherein the three-dimensional current collector substrate is one of a stainless steel mesh, a nickel mesh, a titanium mesh, a copper mesh, and a carbon mesh.
3. The alloy skeletal supported zinc metal negative electrode of claim 1, wherein the zinc-based alloy layer comprises one or more of a zinc-copper alloy and a zinc-silver alloy;
the zinc-copper alloy comprises Cu5Zn8And CuZn5The zinc-silver alloy is AgZn3。
4. A preparation method of an alloy framework supported zinc metal cathode is characterized by comprising the following steps:
step 1: pretreating the three-dimensional current collector substrate;
step 2: preparing a mixed solution containing zinc ions and alloy element ions as an electrolyte;
and step 3: performing deposition treatment on the three-dimensional current collector obtained in the step (1) as a working electrode and a zinc sheet counter electrode in the electrolyte obtained in the step (2) to obtain a modified three-dimensional current collector;
and 4, step 4: and (4) taking the modified three-dimensional current collector obtained in the step (3) as a positive electrode, assembling the positive electrode and a zinc foil into a battery, performing discharge treatment, and realizing the compounding of the modified three-dimensional current collector and zinc to obtain the alloy framework supported zinc metal negative electrode.
5. The preparation method of the alloy framework supported zinc metal negative electrode as claimed in claim 4, wherein the pretreatment specifically comprises: cutting the three-dimensional current collector substrate, then carrying out ultrasonic cleaning by using acid, water and alcohol in sequence, and drying.
6. The method of claim 4, wherein in the electrolyte, the ions of the alloying element comprise one of copper ions and silver ions; the molar concentration ratio of the alloy element ions to the zinc ions is 1: 25-100.
7. The preparation method of the alloy framework supported zinc metal cathode according to claim 4, wherein in the step 3, the deposition current density is 1-9 mA cm-2The deposition time was 5 min.
8. The method for preparing the alloy framework supported zinc metal cathode according to claim 4, wherein in the step 4, the discharge treatment comprises the following steps: 0.2 to 0.4mA cm-2And discharging for 12.5-25 h at constant current.
9. The application of the alloy framework supported zinc metal cathode is characterized in that the alloy framework supported zinc metal cathode as defined in any one of claims 1 to 3 or the alloy framework supported zinc metal cathode prepared by the method as defined in any one of claims 4 to 8 and a zinc foil are assembled into a non-completely symmetrical battery.
10. Alloy framework supported zinc metal cathodeUse of an alloy skeleton-supported zinc metal negative electrode according to any one of claims 1 to 3 or an alloy skeleton-supported zinc metal negative electrode prepared by a method according to any one of claims 4 to 8 as a negative electrode, CNT-MnO2Is used as a positive electrode to assemble the water-system zinc ion battery.
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