CN117587474A - Zinc alloy negative electrode and preparation method and application thereof - Google Patents

Zinc alloy negative electrode and preparation method and application thereof Download PDF

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CN117587474A
CN117587474A CN202311559787.0A CN202311559787A CN117587474A CN 117587474 A CN117587474 A CN 117587474A CN 202311559787 A CN202311559787 A CN 202311559787A CN 117587474 A CN117587474 A CN 117587474A
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zinc
negative electrode
tin
salt
electroplating solution
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方国赵
李明珠
刘哲轩
梁叔全
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Central South University
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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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
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    • 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
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    • 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
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    • H01M2004/027—Negative electrodes
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Abstract

The invention discloses a zinc alloy negative electrode, a preparation method and application thereof, wherein a (002) crystal face of a Zn phase in the zinc alloy negative electrode is mainly oriented, and the weight percentage ratio of Zn to Sn is 85-95: 5-15, namely mixing zinc salt, tin salt, complexing agent and water to obtain electroplating solution; in a constant current mode, electroplating solution is electrodeposited on the surface of a substrate to obtain a zinc-tin binary alloy coating, wherein the molar ratio of zinc salt to tin salt is 40-20: 1. according to the invention, the preferred orientation is combined with alloying, and the zinc-tin binary alloy plating layer with certain characteristics and surface capacity can be unexpectedly obtained by simply regulating and controlling the electroplating solution and the electrodeposition process, so that the zinc-tin alloy negative electrode with the (002) crystal face highly oriented is prepared in one step, is used as a reaction surface of a water-based zinc metal battery, and has excellent electrochemical performance.

Description

Zinc alloy negative electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of water-based zinc metal batteries, and particularly relates to a zinc alloy negative electrode, a preparation method and application thereof.
Background
Rechargeable Aqueous Zinc Ion Batteries (AZIBs) are candidates for emerging energy storage devices due to their high safety, environmental friendliness, low cost, and high capacity. Among them, zinc as a negative electrode has its inherent advantages: compared with other active metal cathodes, the metal zinc has higher stability in an aqueous medium and a humid atmosphere, so that the zinc battery can be directly assembled in a non-protective atmosphere; the moderate standard electrode potential (-0.762 v vs. she) and the higher hydrogen evolution overpotential ensure efficient and reversible zinc deposition/stripping behavior; the oxidation-reduction reaction of two electron transfer endows the metallic zinc with higher volume specific capacity and mass specific capacity which are respectively 5855mAh cm -3 And 820mAh g -1 。
However, zinc cathodes still have a number of key problems: uncontrolled zinc dendrites can puncture the fiberglass separator, eventually leading to a short circuit in the cell; preferential dissolution of dendrite roots may cause dendrites to separate from the host, thereby resulting in "dead zinc" loss of activity and accelerated zinc consumption. In addition, zinc anodes tend to become weak after repeated cycling due to their inherent host-free nature. These structural failures are not repairable, greatly increasing the risk of battery failure. Therefore, developing a negative electrode material with uniform zinc deposition behavior is of great significance for improving the overall performance of AZIBs.
In recent years, many researchers have proposed various solutions from the negative electrode side, including construction of an interface protective layer, design of a three-dimensional structure, and the like. Although these strategies can improve the performance of zinc metal anodes to some extent, they are difficult to continue to function during long periods of cycling. In particular, in-situ and ex-situ coatings are effective only at the surface and it is difficult to ensure interfacial integrity during cycling, three-dimensional structures require complex manufacturing processes and the structural network is prone to deformation and even collapse. There is an urgent need to explore substantial modification measures to fundamentally solve the thermodynamic and kinetic challenges of zinc cathodes.
The metallic zinc has a close-packed hexagonal (hcp) structure, and the atomic structures of different crystal planes are greatly different. Wherein the surface energy of the (002) crystal face is the lowest, the deposition of the (002) crystal face is induced, the formation of a flat morphology is facilitated, and the growth of dendrites is inhibited. At present, researchers mostly utilize electrolyte additives to regulate the preferred orientation of a zinc (002) crystal face, but the strength of the (002) crystal face is slightly improved, and the influence of the additives on the cathode material and the whole battery is not considered on one side. The corrosion reaction of the zinc cathode under the weak acid condition is mainly controlled by hydrogen evolution. When two metals are bonded with each other, the dissolution potential of the non-noble metal can move forward, so that alloying with high hydrogen overpotential metals (such as tin, indium and the like) can effectively improve the corrosion resistance of the zinc alloy. Liu Hong the zinc sheet is soaked in tin salt solution to obtain the negative electrode with zinc-tin alloy interface by utilizing simple displacement reaction, but the content of tin metal is uncontrollable and the surface is uneven under the method.
Disclosure of Invention
Aiming at the problems of low coulombic efficiency and poor cycle stability caused by serious side reaction of a zinc cathode in charge and discharge in the prior art, the invention provides a zinc alloy cathode, a preparation method and application thereof, wherein preferred orientation and alloying are combined, and a zinc-tin binary alloy coating with certain characteristics and surface capacity can be unexpectedly obtained by simply regulating and controlling electroplating liquid and electrodeposition procedures, so that the zinc-tin alloy cathode with highly oriented (002) crystal face is prepared in one step, is used as a reaction surface of a water-based zinc metal battery, and has excellent electrochemical performance.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of zinc alloy negative electrode comprises mixing zinc salt, tin salt, complexing agent and water to obtain electroplating solution; in a constant current mode, electroplating solution is electrodeposited on the surface of a substrate to obtain a zinc-tin binary alloy coating, wherein the molar ratio of zinc salt to tin salt is 40-20: 1.
preferablyThe zinc salt is ZnSO 4 ·7H 2 O、ZnCl 2 Or Zn (CF) 3 SO 3 ) 2 The tin salt is SnSO 4 、SnCl 2 The method comprises the steps of carrying out a first treatment on the surface of the In the electroplating solution, the concentration of zinc salt is 0.1-1 mol/L.
Preferably, the complexing agent is EDTA-2Na, and the concentration of the complexing agent in the electroplating solution is 0.01-0.1 mol/L.
Preferably, the substrate is a copper foil, zinc foil, titanium foil or carbon-based material.
Preferably, the electrodeposit has a current density of 5 to 30mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Further preferably 10 to 20mA/cm 2 。
Preferably, the electrodeposition process is: and (3) taking a zinc sheet as a negative electrode and a copper sheet as a positive electrode, performing constant current electrodeposition in an electrolytic tank, and depositing a zinc-tin binary alloy coating on the copper sheet.
The invention also provides a zinc alloy negative electrode prepared by the preparation method, wherein the (002) crystal face of Zn phase is mainly oriented, and the weight percentage ratio of Zn to Sn is 85-95: 5 to 15.
The invention also provides application of the zinc alloy cathode to preparation of a water-based zinc metal battery.
The invention has the advantages that:
(1) The invention innovatively provides a method for preparing a zinc-tin alloy composite anode material with stronger (002) orientation in one step based on an electrodeposition mode, and by means of cooperative control of zinc-tin mole ratio in electrolyte and current density in the electrodeposition process, a zinc-tin binary alloy coating with high structural stability, good ionic conductivity and good matrix binding force can be formed on the surface of a substrate, and the preferential orientation of a (002) crystal face can be obtained based on the simple preparation method, so that the discharge depth and the circulation stability of the prepared composite anode under high current density can be further improved.
(2) Compared with a plurality of synthetic routes consuming high energy, the preparation method of the zinc alloy induced plating modified zinc cathode provided by the invention is simple, convenient, efficient and short in time consumption, and is beneficial to industrial mass production of the water-based zinc ion battery.
Drawings
FIG. 1 is an XRD pattern of Zn|Sn-1 of example 1, zn-1 of comparative example 1 and Bare Zn of comparative example 3.
FIG. 2 is an XRD pattern of Zn|Sn-2 of example 2, zn-2 of comparative example 2 and Bare Zn of comparative example 3.
FIG. 3 shows XRD patterns of Zn|Sn-1 of example 1, zn|Sn-3 of example 3, and Zn|Sn-4 of example 4.
FIG. 4 is XRD patterns (a) of Zn|Sn-1 of example 1, zn|Sn-5 of comparative example 4 and Zn|Sn-6 of comparative example 5; FIG. b shows a physical pattern of the deposit of Zn|Sn-5 in comparative example 4.
FIG. 5 is a physical view of the plating solution used and the deposit of Zn|Sn-6 of comparative example 6.
FIG. 6 shows the chemical compositions of Zn|Sn-1 of example 1 and Zn|Sn-2 of example 2, as measured by inductively coupled plasma atomic emission spectrometry (ICP).
Fig. 7 is a scan of the deposited anode obtained in example 1 (a), example 2 (b), comparative example 1 (c), and comparative example 2 (d).
FIG. 8 is a graph (a) showing the cycle performance of zinc/zinc symmetric cells of Zn|Sn-1 of example 1, zn-1 of comparative example 1 and Bare Zn of comparative example 3; comparison of zinc/zinc symmetric cell cycle performance of Zn|Sn-2 of example 2, zn-2 of comparative example 2 and Bare Zn of comparative example 3 (b).
FIG. 9 is an XRD pattern (a) of the Zn|Sn-1 symmetric cell of example 1 after corresponding number of cycles; SEM image (b) of the negative side after 50 cycles (50 cycles); SEM image (c) of the negative side after 80 cycles (80 cycles).
FIG. 10 is a graph showing the electrochemical performance of the positive electrode of the ammonium vanadate used for Zn|Sn-1 of example 1, zn|Sn-2 of example 2, and Bare Zn of comparative example 3.
Detailed Description
The invention will now be further illustrated by reference to the accompanying drawings and examples, wherein the starting materials are obtained commercially, and wherein the preparation process according to the invention is conventional in the art unless otherwise specified, and wherein the following examples are intended to illustrate the invention and are not intended to limit the invention further.
Example 1
A method for preparing a (002) oriented zinc-tin binary alloy anode by electrodeposition on a copper substrate, comprising the steps of:
step 1: 11.55024g of zinc sulphate heptahydrate ZnSO was weighed out 4 ·7H 2 O, 0.42954g stannous sulfate SnSO 4 1.8612g of disodium ethylenediamine tetraacetate EDTA-2Na is added into 100ml of deionized water, and stirred and dissolved at normal temperature to obtain electroplating solution;
step 2: cutting the initial copper foil and zinc foil to obtain copper sheets (8 cm x 8 cm) and zinc sheets (8 cm x 8 cm) with fixed sizes, performing surface treatment on the copper sheets and the zinc sheets, removing dust, oil ester, oxide and the like possibly existing by alcohol, and placing the copper sheets and the zinc sheets in a plating tank after deionized water is washed;
step 3: selecting constant current of 20mAcm -2 Electroplating for 15min, and performing an electrodeposition process;
step 4: after the electrodeposition is finished, taking out the deposition side of the positive electrode, washing the positive electrode with deionized water, putting the positive electrode into a drying oven for drying, and taking out the positive electrode to obtain Zn|Sn-1, wherein the deposition surface capacity is 5mAh cm -2 ；
Step 5: a wafer punched with a plating layer of 15mm diameter using a tablet press together with a copper substrate was used as the negative electrode of a zinc ion battery, wherein the deposited layer was used as the reaction surface of the battery.
Example 2
A method for preparing a (002) oriented zinc-tin binary alloy anode by electrodeposition on a copper substrate, comprising the steps of:
step 1: 11.5504g of zinc sulphate heptahydrate ZnSO was weighed out 4 ·7H 2 O, 0.21477g stannous sulfate SnSO 4 1.8612g of disodium ethylenediamine tetraacetate EDTA-2Na is added into 100ml of deionized water, and stirred and dissolved at normal temperature to obtain electroplating solution;
step 2: cutting the initial copper foil and zinc foil to obtain copper sheets (8 cm x 8 cm) and zinc sheets (8 cm x 8 cm) with fixed sizes, performing surface treatment on the copper sheets and the zinc sheets, removing dust, oil ester, oxide and the like possibly existing by alcohol, and placing the copper sheets and the zinc sheets in a plating tank after deionized water is washed;
step 3: selecting constant current of 10mAcm -2 Electroplating for 30min, and performing an electrodeposition process;
step 4: after the electrodeposition is finished, taking out the deposition side of the positive electrode, washing the positive electrode with deionized water, putting the positive electrode into a drying oven for drying, and taking out the positive electrode to obtain Zn|Sn-2, wherein the deposition surface capacity is 5mAh cm -2 ；
Step 5: a wafer punched with a plating layer of 15mm diameter using a tablet press together with a copper substrate was used as the negative electrode of a zinc ion battery, wherein the deposited layer was used as the reaction surface of the battery.
Example 3
A preparation method of a zinc-tin binary alloy anode electrodeposited on a copper substrate comprises the following steps:
step 1: 11.55024g of zinc sulphate heptahydrate ZnSO was weighed out 4 ·7H 2 O, 0.42954g stannous sulfate SnSO 4 1.8612g of disodium ethylenediamine tetraacetate EDTA-2Na is added into 100ml of deionized water, and stirred and dissolved at normal temperature to obtain electroplating solution;
step 2: cutting the initial copper foil and zinc foil to obtain copper sheets (8 cm x 8 cm) and zinc sheets (8 cm x 8 cm) with fixed sizes, performing surface treatment on the copper sheets and the zinc sheets, removing dust, oil ester, oxide and the like possibly existing by alcohol, and placing the copper sheets and the zinc sheets in a plating tank after deionized water is washed;
step 3: selecting constant current 5mAcm -2 Electroplating for 60min, and performing an electrodeposition process;
step 4: after the electrodeposition is finished, taking out the deposition side of the positive electrode, washing the positive electrode with deionized water, putting the positive electrode into a drying oven for drying, and taking out the positive electrode to obtain Zn|Sn-3, wherein the deposition surface capacity is 5mAh cm -2 ；
Step 5: a wafer punched with a plating layer of 15mm diameter using a tablet press together with a copper substrate was used as the negative electrode of a zinc ion battery, wherein the deposited layer was used as the reaction surface of the battery.
Example 4
A preparation method of a zinc-tin binary alloy anode electrodeposited on a copper substrate comprises the following steps:
step 1: 11.55024g of zinc sulphate heptahydrate ZnSO was weighed out 4 ·7H 2 O, 0.42954g sulfuric acidStannous SnSO 4 1.8612g of disodium ethylenediamine tetraacetate EDTA-2Na is added into 100ml of deionized water, and stirred and dissolved at normal temperature to obtain electroplating solution;
step 2: cutting the initial copper foil and zinc foil to obtain copper sheets (8 cm x 8 cm) and zinc sheets (8 cm x 8 cm) with fixed sizes, performing surface treatment on the copper sheets and the zinc sheets, removing dust, oil ester, oxide and the like possibly existing by alcohol, and placing the copper sheets and the zinc sheets in a plating tank after deionized water is washed;
step 3: selecting constant current of 30mAcm -2 Electroplating for 10min, and performing an electrodeposition process;
step 4: after the electrodeposition is finished, taking out the deposition side of the positive electrode, washing the positive electrode with deionized water, putting the positive electrode into a drying oven for drying, and taking out the positive electrode to obtain Zn|Sn-4, wherein the deposition surface capacity is 5mAh cm -2 ；
Step 5: a wafer punched with a plating layer of 15mm diameter using a tablet press together with a copper substrate was used as the negative electrode of a zinc ion battery, wherein the deposited layer was used as the reaction surface of the battery.
Comparative example 1
A method for preparing a zinc metal negative electrode electrodeposited on a copper substrate, comprising the steps of:
step 1: 11.5504g of zinc sulphate heptahydrate ZnSO was weighed out 4 ·7H 2 Adding O and 1.8612g of disodium ethylenediamine tetraacetate EDTA-2Na into 100ml of deionized water, stirring at normal temperature for dissolution to obtain electroplating solution;
step 2: cutting the initial copper foil and zinc foil to obtain copper sheets and zinc sheets with fixed sizes, which can be filled into an electrolytic tank, carrying out surface treatment on the copper sheets and the zinc sheets, removing dust, oil esters, oxides and the like which possibly exist by alcohol, and placing the copper sheets and the zinc sheets in a plating tank after deionized water is washed;
step 3: selecting constant current of 20mAcm -2 Electroplating for 15min, and performing an electrodeposition process;
step 4: after electrodeposition is finished, taking out the deposition side of the positive electrode, washing the positive electrode with deionized water, putting the positive electrode into a drying oven for drying, and taking out the positive electrode to obtain Zn-1, wherein the deposition surface capacity is 5mAh cm -2 ；
Step 5: a wafer punched with a plating layer of 15mm diameter using a tablet press together with a copper substrate was used as the negative electrode of a zinc ion battery, wherein the deposited layer was used as the reaction surface of the battery.
Comparative example 2
A method for preparing a zinc metal negative electrode electrodeposited on a copper substrate, comprising the steps of:
step 1: 11.5504g of zinc sulfate heptahydrate ZnSO was weighed out 4 ·7H 2 Adding O and 1.8612g of disodium ethylenediamine tetraacetate EDTA-2Na into 100ml of deionized water, stirring at normal temperature for dissolution to obtain electroplating solution;
step 2: cutting the initial copper foil and zinc foil to obtain copper sheets and zinc sheets with fixed sizes, which can be filled into an electrolytic tank, carrying out surface treatment on the copper sheets and the zinc sheets, removing dust, oil esters, oxides and the like which possibly exist by alcohol, and placing the copper sheets and the zinc sheets in a plating tank after deionized water is washed;
step 3: selecting constant current of 10mAcm -2 Electroplating for 30min, and performing an electrodeposition process;
step 4: after electrodeposition is finished, taking out the deposition side of the positive electrode, washing the positive electrode with deionized water, putting the positive electrode into a drying oven for drying, and taking out the positive electrode to obtain Zn-2, wherein the deposition surface capacity is 5mAh cm -2 ；
Step 5: a wafer punched with a plating layer of 15mm diameter using a tablet press together with a copper substrate was used as the negative electrode of a zinc ion battery, wherein the deposited layer was used as the reaction surface of the battery.
Comparative example 3
The zinc sheet is purchased from the company of Fabry-Perot, inc. and has a zinc content of 99.9% or more and a surface capacity of about 5mAh cm -2 . A wafer punched into a 15mm diameter by a tablet press is used as the negative electrode of the zinc ion battery.
Comparative example 4
A preparation method of a zinc-tin binary alloy anode electrodeposited on a copper substrate comprises the following steps:
step 1: 11.55024g of zinc sulphate heptahydrate ZnSO was weighed out 4 ·7H 2 O, 0.64431g stannous sulfate SnSO 4 、1.8612g of disodium ethylenediamine tetraacetate EDTA-2Na is added into 100ml of deionized water, and stirred and dissolved at normal temperature to obtain electroplating solution;
step 2: cutting the initial copper foil and zinc foil to obtain copper sheets (8 cm x 8 cm) and zinc sheets (8 cm x 8 cm) with fixed sizes, performing surface treatment on the copper sheets and the zinc sheets, removing dust, oil ester, oxide and the like possibly existing by alcohol, and placing the copper sheets and the zinc sheets in a plating tank after deionized water is washed;
step 3: selecting constant current of 20mAcm -2 Electroplating for 15min, and performing an electrodeposition process;
step 4: after the electrodeposition is finished, taking out the deposition side of the positive electrode, washing the positive electrode with deionized water, putting the positive electrode into a drying oven for drying, and taking out the positive electrode to obtain Zn|Sn-5, wherein the deposition surface capacity is 5mAh cm -2 ；
Step 5: a wafer punched with a plating layer of 15mm diameter using a tablet press together with a copper substrate was used as the negative electrode of a zinc ion battery, wherein the deposited layer was used as the reaction surface of the battery.
Comparative example 5
A preparation method of a zinc-tin binary alloy anode electrodeposited on a copper substrate comprises the following steps:
step 1: 11.55024g of zinc sulphate heptahydrate ZnSO was weighed out 4 ·7H 2 O, 0.10739g stannous sulfate SnSO 4 1.8612g of disodium ethylenediamine tetraacetate EDTA-2Na is added into 100ml of deionized water, and stirred and dissolved at normal temperature to obtain electroplating solution;
step 2: cutting the initial copper foil and zinc foil to obtain copper sheets (8 cm x 8 cm) and zinc sheets (8 cm x 8 cm) with fixed sizes, performing surface treatment on the copper sheets and the zinc sheets, removing dust, oil ester, oxide and the like possibly existing by alcohol, and placing the copper sheets and the zinc sheets in a plating tank after deionized water is washed;
step 3: selecting constant current of 20mAcm -2 Electroplating for 15min, and performing an electrodeposition process;
step 4: after the electrodeposition is finished, taking out the deposition side of the positive electrode, washing the positive electrode with deionized water, putting the positive electrode into a drying oven for drying, and taking out the positive electrode to obtain Zn|Sn-6, wherein the deposition surface capacity is 5mAh cm -2 ；
Step 5: a wafer punched with a plating layer of 15mm diameter using a tablet press together with a copper substrate was used as the negative electrode of a zinc ion battery, wherein the deposited layer was used as the reaction surface of the battery.
Comparative example 6
A preparation method of a zinc-tin binary alloy anode electrodeposited on a copper substrate comprises the following steps:
step 1: 11.55024g of zinc sulphate heptahydrate ZnSO was weighed out 4 ·7H 2 O, 0.10739g stannous sulfate SnSO 4 Adding the solution into 100ml of deionized water, stirring and dissolving at normal temperature to obtain electroplating solution;
step 2: cutting the initial copper foil and zinc foil to obtain copper sheets (8 cm x 8 cm) and zinc sheets (8 cm x 8 cm) with fixed sizes, performing surface treatment on the copper sheets and the zinc sheets, removing dust, oil ester, oxide and the like possibly existing by alcohol, and placing the copper sheets and the zinc sheets in a plating tank after deionized water is washed;
step 3: selecting constant current of 20mAcm -2 Electroplating for 15min, and performing an electrodeposition process;
step 4: after the electrodeposition is finished, taking out the deposition side of the positive electrode, washing the positive electrode with deionized water, putting the positive electrode into a drying oven for drying, and taking out the positive electrode to obtain Zn|Sn-7, wherein the deposition surface capacity is 5mAh cm -2 ；
Step 5: a wafer punched with a plating layer of 15mm diameter using a tablet press together with a copper substrate was used as the negative electrode of a zinc ion battery, wherein the deposited layer was used as the reaction surface of the battery.
As shown in FIG. 1, in the XRD patterns of example 1 (Zn|Sn-1), comparative example 1 (Zn-1) and comparative example 3 (Bare Zn), the deposition of comparative example 1 (Zn-1) gave zinc metal, and the orientation of the deposited zinc metal (002) was significantly improved with respect to the ordinary commercially available zinc sheet (Bare Zn), while in example 1 (Zn|Sn-1), four lower peaks corresponding to Sn phase (PDF#04-0673) were present, and the (002) crystal plane peak of Zn phase was significantly enhanced.
As shown in FIG. 2, in the XRD patterns of example 2 (Zn|Sn-2), comparative example 2 (Zn-2) and comparative example 3 (Bare Zn), the deposition of comparative example 1 (Zn-2) gave zinc metal, and the orientation of the deposited zinc metal (002) was significantly improved with respect to the ordinary commercially available zinc sheet (Bare Zn), while in example 2 (Zn|Sn-2), four lower peaks corresponding to Sn phase (PDF#04-0673) were present, and the (002) crystal plane peak of Zn phase was significantly enhanced.
As shown in FIG. 3, XRD patterns of example 1 (Zn|Sn-1), example 3 (Zn|Sn-3) and example 4 (Zn|Sn-4) were measured at 5-30mAcm -2 Can obtain (002) oriented zinc-tin binary alloy under the current density of 10-20mAcm -2 In this case, the (002) plane peak intensity is more excellent.
As shown in FIG. 4, (a) is an XRD pattern of example 1 (Zn|Sn-1), comparative example 4 (Zn|Sn-5) and comparative example 5 (Zn|Sn-6), and (b) is a physical pattern of the deposited coating of comparative example 4 (Zn|Sn-5), when the mole of zinc salt and tin salt are relatively low, although (002) oriented zinc-tin binary alloy can be obtained, the surface of the deposited coating is covered by a loose structure substance, the adhesion to the substrate is low, and the quality of such coating is low and cannot be applied to the negative electrode material of the water-based zinc-ion battery; on the other hand, when the molar ratio of zinc salt to tin salt is relatively high, a zinc-tin alloy having (002) orientation cannot be obtained at this time, and the intended effect is not achieved.
As shown in FIG. 5, a physical diagram of the plating solution and the deposit of comparative example 6 (Zn|Sn-7), sn when no complex is added 2+ The plating layer is extremely easy to hydrolyze in aqueous solution, so that the plating solution is turbid and cannot be used normally, and even if the plating solution is used, the deposited plating layer is basically a by-product with poor crystallinity and loose structure, and cannot be applied to the negative electrode material of the water-based zinc ion battery.
As shown in fig. 6, the chemical compositions of the zinc alloy negative electrode (zn|sn-1) obtained in example 1 and the zinc alloy negative electrode (zn|sn-2) obtained in example 2 were measured by inductively coupled plasma atomic emission spectrometry (ICP). Analysis revealed that tin metal was successfully deposited into zinc matrix due to stannous sulfate SnSO in the electroplating solution of example 1 4 The concentration was twice that of example 2, and the tin element content in example 1 (Zn|Sn-1) was about twice that of example 2 (Zn|Sn-2) in the ZnSn alloy anode obtained by deposition, in accordance with the expected results.
As shown in FIG. 7, a is the composition of example 1 (Zn|Sn)-1) the scan, b the scan of example 2 (Zn|Sn-2), c the scan of comparative example 1 (Zn-1), d the scan of comparative example 2 (Zn-2). As can be seen from the scan analysis, when Sn-free is used 2+ The zinc metal is deposited to form a uniform sheet distribution on the copper substrate. When Sn is added into the electroplating solution 2+ And when the hexagonal prism is obtained by deposition. Initially Zn 2+ Reduced to Zn, and uniformly distributed on the copper substrate. At the same time accompanied by Sn 2+ And (3) carrying out reduction deposition to obtain Sn metal, guiding Zn screw dislocation to grow as a subsequent nucleation site, and finally growing zinc-tin alloy into a hexagonal prism shape. Wherein the hexagonal prism morphology is more pronounced in example 1 (Zn|Sn-1), illustrating that when Sn 2+ The effect on nucleation growth of zinc is more pronounced with increasing concentration.
As shown in FIG. 8, a is a graph of cycle performance of zinc-symmetric cells of example 1 (Zn|Sn-1), comparative example 1 (Zn-1) and comparative example 3 (Bare Zn). b is a graph of zinc symmetrical cell cycle performance for example 2 (zn|sn-2), comparative example 2 (Zn-2) and comparative example 3 (Bare Zn). In example 1, the current density was 5mAcm –2 The zn|sn-1 negative symmetric battery exhibited a lower initial hysteresis voltage of 50mV and was able to cycle stably for 2800 hours under conditions (negative utilization up to 20%). After 2800 hours, the hysteresis voltage is only 52mV. The initial hysteresis voltage of the Zn-1 cathode is 48mV, but the hysteresis voltage is obviously increased along with the increase of the cycle time, and the short circuit phenomenon occurs due to unavoidable dendrite problems after 500 hours. In example 2, the current density was 5mAcm –2 The initial hysteresis voltage of the Zn|Sn-2 negative electrode symmetrical battery is 55mV, which is higher than Zn|Sn-1 but obviously lower than Zn-2 (60 mV). After 700h, the hysteresis voltage of the Zn|Sn-2 symmetric battery is in a descending trend and stably circulates for 2000h, and the phenomenon of short circuit occurs only when Zn-2 is stably circulated for 580 h. The initial hysteresis voltage of the pure zinc cathode is 89.9mV, and finally, a short circuit occurs after 220 hours. The symmetrical cell demonstrates the advantage of the zinc-tin alloy of the present invention in reversible zinc migration: with lower nucleation barriers and faster charge transfer. After cycling for more than 220 hours, the voltage profile of the comparative example shows significant fluctuations, which are typically characteristic of severe hydrogen evolution reactions. Which is a kind ofThe voltage curve approximates a square wave, which indicates that a short circuit has occurred inside the cell, most likely due to dendrite growth. In contrast, the symmetric cell with zn|sn alloy as electrode accumulated deposition/stripping for longer periods of time exceeding 2000 hours, the voltage profile remained stable without significant polarization. In addition, the depth of discharge of the zinc cathode is an important index for evaluating the practical application of the zinc ion battery, and the high depth of discharge has important significance for improving the overall energy density of the battery. The cycle performance at 20% depth of discharge, even under such severe test conditions, is still capable of cycling zn|sn alloys for more than 2000 hours, which is almost 10 times the Bare Zn cycle life.
As shown in fig. 9, a is an XRD pattern of the negative electrode stripping side after 20 cycles (20 cycles), 50 cycles (50 cycles), 80 cycles (80 cycles) of the symmetric battery of example 1 (zn|sn-1), respectively; b is an SEM image of the negative side after 50 cycles; c is an SEM image of the negative side after 80 cycles. As can be seen from XRD pattern analysis, the Zn|Sn-1 alloy negative electrode can well maintain the (002) orientation even though the symmetric cell is matched with 2M ZnSO4 electrolyte. From the b and c diagrams, it can be seen that the columnar structure can be maintained after circulation, and the stability of the structure is shown. The Zn|Sn alloy maintains a smooth and compact morphology during the whole deposition/stripping process, which indicates that the nucleation and growth processes are more stable.
As shown in fig. 10, a is a full cell performance map of example 1 (zn|sn-1) and comparative example 3 (pore Zn), and b is a full cell performance map of example 2 (zn|sn-2) and comparative example 3 (pore Zn). In terms of long-cycle stability, even at 1Ag -1 At low current densities of (3) the full cell matching the deposited zn|sn alloy can still be cycled stably close to 3000 turns. However, when bare zinc is used, the full cell is cycled only 500 times, and its capacity retention rate is reduced to 80% or less. The excellent long-cycling stability can be attributed to the stable interface of the alloy on the negative side. Even after 1000 cycles in the full cell, the zn|sn alloy still showed a flat and dense surface morphology. In contrast, bare zinc exhibits uncontrolled zinc deposition/stripping, increasing interface impedance, resulting in battery capacity degradation.

Claims (9)

1. A preparation method of a zinc alloy negative electrode is characterized by comprising the following steps: mixing zinc salt, tin salt, complexing agent and water to obtain electroplating solution; in a constant current mode, electroplating solution is electrodeposited on the surface of a substrate to obtain a zinc-tin binary alloy coating, wherein the molar ratio of zinc salt to tin salt is 40-20: 1.
2. the method of manufacturing according to claim 1, characterized in that: the zinc salt is ZnSO 4 ·7H 2 O、ZnCl 2 Or Zn (CF) 3 SO 3 ) 2 The tin salt is SnSO 4 、SnCl 2 The method comprises the steps of carrying out a first treatment on the surface of the In the electroplating solution, the concentration of zinc salt is 0.1-1 mol/L.
3. The method of manufacturing according to claim 1, characterized in that: the complexing agent is EDTA-2Na, and the concentration of the complexing agent in the electroplating solution is 0.01-0.1 mol/L.
4. The method of manufacturing according to claim 1, characterized in that: the base material is copper foil, zinc foil, titanium foil or carbon-based material.
5. The method of manufacturing according to claim 1, characterized in that: the current density of the electrodeposition is 5-30 mA/cm 2 。
6. The method of manufacturing according to claim 5, wherein: the current density of the electrodeposition is 10-20 mA/cm 2 。
7. The method of manufacturing according to claim 1, characterized in that: the electrodeposition process is as follows: and (3) taking a zinc sheet as a negative electrode and a copper sheet as a positive electrode, performing constant current electrodeposition in an electrolytic tank, and depositing a zinc-tin binary alloy coating on the copper sheet.
8. The zinc alloy negative electrode produced by the production method according to any one of claims 1 to 7, characterized in that: the (002) crystal face of Zn phase in the zinc alloy cathode is mainly oriented, and the weight percentage ratio of Zn to Sn is 85-95: 5 to 15.
9. Use of a zinc alloy negative electrode according to claim 8, characterized in that: the method is applied to the preparation of the water-based zinc metal battery.
CN202311559787.0A 2023-11-22 2023-11-22 Zinc alloy negative electrode and preparation method and application thereof Pending CN117587474A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117878238A (en) * 2024-03-12 2024-04-12 中国科学技术大学苏州高等研究院 Single (002) texture zinc metal negative electrode and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117878238A (en) * 2024-03-12 2024-04-12 中国科学技术大学苏州高等研究院 Single (002) texture zinc metal negative electrode and preparation method and application thereof
CN117878238B (en) * 2024-03-12 2024-05-28 中国科学技术大学苏州高等研究院 Single (002) texture zinc metal negative electrode and preparation method and application thereof

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