KR20210147478A - Anode for rechargeable aqueous zinc-ion battery comprising small amount of different element and method of fabricating same - Google Patents

Abstract

Disclosed are a negative electrode for an aqueous zinc secondary battery containing a small amount of a dissimilar metal element and a method for manufacturing the same. The negative electrode is provided to be used in an aqueous zinc secondary battery and includes zinc (Zn) and a heterogeneous element so that corrosion potential is increased higher than that of zinc, therefore a side reaction of the negative electrode can be fundamentally suppressed. In addition, provided is an aqueous zinc secondary battery capable of suppressing high self-discharge by including the negative electrode.

Description

Anode for an aqueous zinc secondary battery containing a small amount of heterogeneous elements and a method for manufacturing the same

The present invention relates to a negative electrode for a water-based zinc secondary battery containing a small amount of a heterogeneous element and a method for manufacturing the same, and the negative electrode prepared according to the present invention contains zinc and a small amount of a heterogeneous metal element, so that when used in an aqueous zinc secondary battery, corrosion and Self-discharge can be suppressed.

Aqueous zinc secondary batteries use zinc with a high theoretical capacity (820 mAh/g) while being 7 times cheaper than lithium, and there is no risk of ignition by using water as an electrolyte solvent. Currently, research on the development of high-capacity cathode materials is currently in progress at home and abroad, and the Korea Electric Power Research Institute has selected it as a "second-generation ESS (Energy Storage System) secondary battery" and research for commercialization has been underway since 2017.

However, the aqueous zinc secondary battery has a problem in that a very high self-discharge (60% or more based on 72 hours) occurs due to side reactions such as insufficient chemical resistance of the zinc negative electrode to the aqueous electrolyte and adsorption with the anode effluent.

Therefore, research on a zinc anode capable of suppressing a side reaction and a method for manufacturing the same is required due to a high corrosion potential in an aqueous zinc secondary battery.

An object of the present invention is to solve the above problems, and to provide a negative electrode of a water-based zinc secondary battery, which is a safe and eco-friendly next-generation battery for electric vehicles and ESS, and a method for manufacturing the same.

Another object of the present invention is to provide a zinc anode for an aqueous zinc secondary battery capable of suppressing side reactions due to high chemical resistance and corrosion potential to the aqueous electrolyte, and a method for manufacturing the same.

In addition, it is to provide an aqueous zinc secondary battery capable of suppressing high self-discharge by including the zinc negative electrode.

According to one aspect of the present invention, the conductive substrate 100; and a zinc alloy layer 200 positioned on the conductive substrate and including a zinc alloy having zinc (Zn) 210 and a heterogeneous element 220; a negative electrode 10 for use in an aqueous zinc secondary battery ) is provided.

In addition, the zinc alloy is 85 to 99% by weight of zinc; and 1 to 15% by weight of heteroelements.

In addition, the heterogeneous element may include at least one selected from the group consisting of nickel (Ni), copper (Cu), iron (Fe), tungsten (W), and cobalt (Co).

In addition, the heterogeneous element may include at least one selected from the group consisting of nickel (Ni), copper (Cu), and iron (Fe).

In addition, the heteroelement may include nickel (Ni).

In addition, the conductive substrate is a titanium foil (Ti foil), titanium foam (Ti foam), carbon nanotubes (CNT), carbon nanofiber (carbon nanofiber), carbon fiber (carbon fiber), graphene foam (graphene foam) and It may include at least one selected from the group consisting of graphene fibers.

According to another aspect of the present invention, the positive electrode; An anode comprising a conductive substrate and a zinc alloy layer disposed on the conductive substrate and including zinc (Zn) and a zinc alloy having a heterogeneous element; a separator positioned between the anode and the cathode; and an aqueous electrolyte; an aqueous zinc secondary battery comprising a.

In addition, the zinc alloy is 85 to 99% by weight of zinc; and 1 to 15% by weight of heteroelements.

In addition, the heterogeneous element may include at least one selected from the group consisting of nickel (Ni), copper (Cu), iron (Fe), tungsten (W), and cobalt (Co).

In addition, the anode may include at least one selected from the group consisting _{of MnO 2} , V ₂ O ₅ , ZnMn ₂ O ₄ , ZnCo ₂ O _{4 and metal vanadates.}

In addition, the separator may include at least one selected from the group consisting of filter paper, glass fiber, polyolefin, and polymer series.

In addition, the aqueous electrolyte may include at least one selected from the group consisting _{of C 2} F ₆ O ₆ S ₂ Zn, CoSO ₄ , MnSO ₄ , Mn(CF ₃ SO ₃ ) ₂ and Na ₂ SO _{4 .}

According to another aspect of the present invention, (a) preparing a plating solution comprising a zinc precursor, a heteroelement precursor and an additive; and (b) putting a conductive substrate and a counter electrode in the plating solution, and applying an electric current to the conductive substrate and the counter electrode. A method of manufacturing a negative electrode for use in an aqueous zinc secondary battery comprising; plating is provided.

In addition, the zinc precursor is zinc chloride (ZnCl ₂ ), zinc nitrate (Zn(NO ₃ ) ₂ ), zinc sulfate (ZnSO ₄ ), zinc acetate (Zn(CH ₃ CO ₂ ) ₂ ) and hydrates thereof. It may include one or more selected from.

In addition, the heteroelement precursor may include at least one selected from the group consisting of a nickel precursor, a copper precursor, an iron precursor, a tungsten precursor, and a cobalt precursor.

In addition, the heteroelement precursor may include at least one selected from the group consisting of a nickel precursor, a copper precursor, and an iron precursor.

In addition, the heteroelement precursor may include a nickel precursor.

In addition, the nickel precursor is nickel chloride (NiCl ₂ ), nickel nitrate (Ni(NO ₃ ) ₂ ), nickel sulfate (NiSO ₄ ), nickel acetate (Ni(CH ₃ CO ₂ ) ₂ ) and a group consisting of hydrates thereof and at least one selected from the group consisting of, wherein the copper precursor is copper chloride (CuCl ₂ ), copper nitrate (Cu(NO ₃ ) ₂ ), copper sulfate (CuSO ₄ ), copper acetate (Cu(CH ₃ CO ₂ ) ₂ ) and and at least one selected from the group consisting of hydrates thereof, wherein the iron precursor is iron chloride (FeCl ₂ ), iron nitrate (Fe(NO ₃ ) ₂ ), iron sulfate (FeSO ₄ ), iron acetate (Fe(CH _{3 )} CO ₂ ) ₂ ) and at least one selected from the group consisting of hydrates thereof, wherein the tungsten precursor is sodium tungstate (Na ₂ WO ₄ ), ammonium paratungstate ((NH ₄ ) ₁₀ (H ₂ W _{12 )} O ₄₂ )), potassium tungstate (K ₂ O ₂ W), and at least one selected from the group consisting of hydrates thereof, wherein the cobalt precursor is cobalt chloride (CoCl ₂ ), cobalt nitrate (Co(NO ₃ ) ₂ ), cobalt sulfate (CoSO ₄ ), cobalt acetate (Co(CH ₃ CO ₂ ) ₂ ), and hydrates thereof may include at least one selected from the group consisting of.

In addition, the additive may include at least one selected from the group consisting of a pH buffering agent, a dispersing agent, and an electrodeposition uniformity improving agent.

In addition, the pH buffer is boric acid (H ₃ BO ₃ ), citric acid (C ₆ H ₈ O ₇ ), potassium citrate (K ₃ (C ₆ H ₅ O ₇ )), sodium citrate (Na ₃ (C ₆ H ₅ O) ₇ )), calcium citrate (Ca ₃ (C ₆ H ₅ O ₇ )), oxalic _{acid (C 2} H ₂ O ₄ ), pyrophosphoric acid (Na ₄ P ₂ O ₇ ), and one selected from the group consisting of hydrates thereof Including the above, wherein the dispersing agent is pyridine (C ₅ H ₅ N), sodium dodecyl sulfate (NaC ₁₂ H ₂₅ SO ₄ ), sodium dodecylbenzenesulfonate (C ₁₈ H ₂₉ NaO ₃ S), pluronic F127 (Pluronic) F127) and at least one selected from the group consisting of hydrates thereof, and the electrodeposition uniformity improving agent is sodium chloride (NaCl), sodium nitrate (NaNO ₃ ), sodium carbonate (NaCO ₃ ), sodium sulfate (NaSO ₄ ), and their It may include one or more selected from the group consisting of hydrates.

In addition, in the plating solution, the sum of the concentrations of the zinc precursor and the heteroelement precursor may be 10 to 150 g/L.

In addition, the plating solution may have a concentration of 0.1 to 200 g/L of the additive.

In addition, the conductive substrate is a titanium foil (Ti foil), titanium foam (Ti foam), carbon nanotubes (CNT), carbon nanofiber (carbon nanofiber), carbon fiber (carbon fiber), graphene foam (graphene foam) and one or more selected from the group consisting of graphene fibers, wherein the counter electrode is one selected from the group consisting of graphite, graphite rod, platinum and glassy carbon It may include more than one species.

Also, in step (b), the density of the current may be ^{1 to 200 mA/cm 2 .}

In addition, the method of manufacturing the negative electrode may further include, after step (b), (c) washing and drying the zinc alloy layer plated on the conductive substrate.

The present invention can provide a negative electrode of a water-based zinc secondary battery, which is a safe and eco-friendly next-generation battery for electric vehicles and ESS, and a method for manufacturing the same.

In addition, since the negative electrode for a water-based zinc secondary battery of the present invention is manufactured through electroplating, a small amount of heterogeneous elements is contained, and the corrosion potential is increased compared to zinc, thereby fundamentally suppressing side reactions of the negative electrode.

In addition, the aqueous zinc secondary battery of the present invention can suppress high self-discharge by including the negative electrode for the aqueous zinc secondary battery.

In addition, the present invention can suppress the corrosion of the negative electrode and the high self-discharge of the aqueous zinc secondary battery, so that it is possible to commercialize the aqueous zinc secondary battery.

Since these drawings are for reference in describing an exemplary embodiment of the present invention, the technical spirit of the present invention should not be construed as being limited to the accompanying drawings.
1 is a schematic diagram showing a negative electrode according to an embodiment of the present invention.
2 is a process flowchart illustrating a method of manufacturing an anode according to an embodiment of the present invention.
3 shows the life test results of Device Examples 1 to 3 and Device Comparative Example 1. FIG.
Figure 4a shows an SEM image of the surface of the negative electrode (Comparative Example 1) after the life test.
4B shows an SEM image of the surface of the negative electrode (Example 1) after the life test.
Figure 4c shows an SEM image of the surface of the negative electrode (Example 2) after the life test.
4D shows an SEM image of the surface of the negative electrode (Example 3) after the life test.
Figure 5 shows the voltage retention performance results when prepared as a symmetric cell using Example 3 as an anode and a cathode, respectively, after preparing two.
6 shows the life test results of Device Examples 4 and 5.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art can easily carry out the present invention.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that detailed descriptions of related known technologies may obscure the gist of the present invention in describing the present invention, the detailed description thereof will be omitted. .

The terminology used herein is used only to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, element, or combination thereof described in the specification exists, and includes one or more other features or It should be understood that the existence or addition of numbers, steps, acts, elements, or combinations thereof, is not precluded in advance.

In addition, terms including ordinal numbers such as first, second, etc. to be used below may be used to describe various elements, but the elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

In addition, when it is said that a certain component is "formed" or "stacked" on another component, it may be formed or laminated by being directly attached to the front surface or one surface on the surface of the other component, but in the middle It should be understood that there may be other components in the .

Hereinafter, the negative electrode for an aqueous zinc secondary battery containing a small amount of a dissimilar metal element of the present invention and a method for manufacturing the same will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

1 is a schematic diagram showing a negative electrode according to an embodiment of the present invention.

Referring to Figure 1, the present invention is a zinc conductive substrate 100; and a zinc alloy layer 200 positioned on the conductive substrate and including a zinc alloy having zinc (Zn) 210 and a heterogeneous element 220; a negative electrode 10 for use in an aqueous zinc secondary battery ) is provided.

In detail, there is provided a negative electrode for a water-based secondary battery capable of fundamentally suppressing a side reaction of the negative electrode by containing a small amount of a heterogeneous element in zinc, thereby increasing the corrosion potential compared to zinc.

In addition, the zinc alloy is 85 to 99% by weight of zinc; and 1 to 15% by weight of heteroelements. When the zinc alloy exceeds 99 wt% (less than 1 wt% of the heteroelement) of zinc, it is not preferable because the effect of increasing the corrosion potential of the negative electrode cannot be obtained by including the heteroelement, and less than 85 wt% of zinc (the heteroelement 15) % by weight), it is not preferable because it is difficult to stably supply zinc ions used as an active material.

In addition, the heterogeneous element may include at least one selected from the group consisting of nickel (Ni), copper (Cu), iron (Fe), tungsten (W), and cobalt (Co), preferably nickel (Ni) ), may include at least one selected from the group consisting of copper (Cu) and iron (Fe), and more preferably include nickel (Ni).

In addition, the conductive substrate is a titanium foil (Ti foil), titanium foam (Ti foam), carbon nanotubes (CNT), carbon nanofiber (carbon nanofiber), carbon fiber (carbon fiber), graphene foam (graphene foam) and It may include one or more selected from the group consisting of graphene fibers, preferably titanium foil (Ti foil).

According to another aspect of the present invention, the positive electrode; An anode comprising a conductive substrate and a zinc alloy layer disposed on the conductive substrate and including zinc (Zn) and a zinc alloy having a heterogeneous element; a separator positioned between the anode and the cathode; and an aqueous electrolyte; an aqueous zinc secondary battery comprising a.

In addition, the zinc alloy is 85 to 99% by weight of zinc; and 1 to 15% by weight of heteroelements. When the zinc alloy exceeds 99 wt% (less than 1 wt% of the heteroelement) of zinc, it is not preferable because the effect of increasing the corrosion potential of the negative electrode cannot be obtained by including the heteroelement, and less than 85 wt% of zinc (the heteroelement 15) % by weight), it is not preferable because it is difficult to stably supply zinc ions used as an active material.

In addition, the heterogeneous element may include at least one selected from the group consisting of nickel (Ni), copper (Cu), iron (Fe), tungsten (W), and cobalt (Co), preferably nickel (Ni) ), may include at least one selected from the group consisting of copper (Cu) and iron (Fe), and more preferably include nickel (Ni).

In addition, the anode may include at least one selected from the group consisting _{of MnO 2} , V ₂ O ₅ , ZnMn ₂ O ₄ , ZnCo ₂ O _{4 and metal vanadates, preferably MnO 2} .

In addition, the separator may include one or more selected from the group consisting of filter paper, glass fiber, polyolefin and polymer series, preferably filter paper. may include

In addition, the aqueous electrolyte may include at least one selected from the group consisting _{of C 2} F ₆ O ₆ S ₂ Zn, CoSO ₄ , MnSO ₄ , Mn(CF ₃ SO ₃ ) ₂ and Na ₂ SO _{4 , preferably} For example, C ₂ F ₆ O ₆ S ₂ Zn may be included.

2 is a process flowchart illustrating a method of manufacturing an anode according to an embodiment of the present invention.

Referring to FIG. 2 , the present invention includes the steps of: (a) preparing a plating solution including a zinc precursor, a heteroelement precursor, and an additive; and (b) putting a conductive substrate and a counter electrode in the plating solution, and applying an electric current to the conductive substrate and the counter electrode. It provides a method of manufacturing a negative electrode for use in a water-based zinc secondary battery, comprising the step of plating.

In detail, by using an alloying technique using electroplating, a small amount of dissimilar metal is included in zinc to increase the corrosion potential of zinc to synthesize a zinc alloy capable of suppressing corrosion of zinc in an aqueous electrolyte, wherein the zinc alloy is It can be used as a negative electrode for a water-based zinc secondary battery.

In addition, the zinc precursor is zinc chloride (ZnCl ₂ ), zinc nitrate (Zn(NO ₃ ) ₂ ), zinc sulfate (ZnSO ₄ ), zinc acetate (Zn(CH ₃ CO ₂ ) ₂ ) and hydrates thereof. It may include at least one selected from the group consisting of, preferably zinc chloride (ZnCl ₂ ).

In addition, the heteroelement precursor may include at least one selected from the group consisting of a nickel precursor, a copper precursor, an iron precursor, a tungsten precursor, and a cobalt precursor, preferably from the group consisting of a nickel precursor, a copper precursor, and an iron precursor It may include at least one selected type, and more preferably include a nickel precursor.

In addition, the nickel precursor is nickel chloride (NiCl ₂ ), nickel nitrate (Ni(NO ₃ ) ₂ ), nickel sulfate (NiSO ₄ ), nickel acetate (Ni(CH ₃ CO ₂ ) ₂ ) and hydrates thereof from the group consisting of It may include one or more selected from, preferably nickel chloride (NiCl ₂ ).

In addition, the copper precursor is copper chloride (CuCl ₂ ), copper nitrate (Cu(NO ₃ ) ₂ ), copper sulfate (CuSO ₄ ), copper acetate (Cu(CH ₃ CO ₂ ) ₂ ) and hydrates thereof from the group consisting of It may include one or more selected from, more preferably copper chloride (CuCl ₂ ).

In addition, the iron precursor is iron chloride (FeCl ₂ ), iron nitrate (Fe(NO ₃ ) ₂ ), iron sulfate (FeSO ₄ ), iron acetate (Fe(CH ₃ CO ₂ ) ₂ ) and hydrates thereof from the group consisting of It may include one or more selected from, more preferably iron chloride (FeCl ₂ ).

In addition, the tungsten precursor is sodium tungstate (Na ₂ WO ₄ ), ammonium paratungstate ((NH ₄ ) ₁₀ (H ₂ W ₁₂ O ₄₂ )), potassium tungstate (K ₂ O ₂ W), and hydrates thereof It may include one or more selected from the group consisting of.

In addition, the cobalt precursor is cobalt chloride (CoCl ₂ ), cobalt nitrate (Co(NO ₃ ) ₂ ), cobalt sulfate (CoSO ₄ ), cobalt acetate (Co(CH ₃ CO ₂ ) ₂ ) and hydrates thereof. It may include one or more selected from.

In addition, the additive may include at least one selected from the group consisting of a pH buffering agent, a dispersing agent, and an electrodeposition uniformity improving agent.

In addition, the pH buffer is boric acid (H ₃ BO ₃ ), citric acid (C ₆ H ₈ O ₇ ), potassium citrate (K ₃ (C ₆ H ₅ O ₇ )), sodium citrate (Na ₃ (C ₆ H ₅ O) ₇ )), calcium citrate (Ca ₃ (C ₆ H ₅ O ₇ )), oxalic _{acid (C 2} H ₂ O ₄ ), pyrophosphoric acid (Na ₄ P ₂ O ₇ ), and one selected from the group consisting of hydrates thereof may include more, preferably boric acid (H ₃ BO ₃ ), citric acid (C ₆ H ₈ O ₇ ), potassium citrate (K ₃ (C ₆ H ₅ O ₇ )), sodium citrate (Na ₃ (C ₆ H ₅ O ₇ )) and calcium citrate (Ca ₃ (C ₆ H ₅ O ₇ )) may include at least one selected from the group consisting of, more preferably boric acid (H ₃ BO ₃ ) and potassium citrate (K ₃ (C ₆ H ₅ O ₇ )) It may include one or more selected from the group consisting of.

In addition, the dispersant is pyridine (C ₅ H ₅ N), sodium dodecyl sulfate (NaC ₁₂ H ₂₅ SO ₄ ), sodium dodecylbenzenesulfonate (C ₁₈ H ₂₉ NaO ₃ S), pluronic F127 (Pluronic F127) and It may include at least one selected from the group consisting of hydrates thereof, and preferably sodium dodecyl sulfate (NaC ₁₂ H ₂₅ SO ₄ ).

In addition, the electrodeposition uniformity improving agent may include at least one selected from the group consisting of sodium chloride (NaCl), sodium nitrate (NaNO ₃ ), sodium carbonate (NaCO ₃ ), sodium sulfate (NaSO _{4 ), and hydrates thereof, preferably} For example, sodium chloride (NaCl) may be included.

In addition, in the plating solution, the sum of the concentrations of the zinc precursor and the heteroelement precursor may be 10 to 150 g/L, preferably 20 to 100 g/L, and more preferably 40 to 80 g It can be /L.

When the sum of the concentrations of the zinc precursor and the heteroelement precursor is less than 10 g/L, the plating speed is too slow, which is undesirable. and the plating cost increases, which is undesirable.

In addition, in the plating solution, the concentration of the additive may be 0.1 to 200 g/L, preferably 1 to 50 g/L. When the concentration of the additive is less than 0.1 g/L, it is undesirable due to the lack of additives and difficulty in forming a uniform plating. Not desirable.

In addition, the conductive substrate is a titanium foil (Ti foil), titanium foam (Ti foam), carbon nanotubes (CNT), carbon nanofiber (carbon nanofiber), carbon fiber (carbon fiber), graphene foam (graphene foam) and It may include one or more selected from the group consisting of graphene fibers, preferably titanium foil (Ti foil).

In addition, the counter electrode may include at least one selected from the group consisting of graphite, a graphite rod, platinum and glassy carbon, and preferably includes graphite. can do.

In addition, in step (b), the density of the current may be 1 to 200 mA/cm ² , preferably 30 to 100 mA/cm ² , more preferably 50 to 80 mA/cm ² . .

When the density of the current is ^{less than 1 mA/cm 2} , the plating formation time is too slow, which is not preferable, and ^{when it exceeds 200 mA/cm 2} , it is not preferable because the limit current density is reached and the plating efficiency rapidly drops.

In addition, the method of manufacturing the negative electrode may further include, after step (b), (c) washing and drying the zinc alloy layer plated on the conductive substrate.

[Example]

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes, and the scope of the present invention is not limited thereto.

Anode for water-based zinc secondary battery

Example 1: Zinc alloy containing 3 wt% of Ni

Zinc chloride (ZnCl ₂ ) 50 g/L as _{zinc precursor, nickel chloride (NiCl 2} ) 5 g/L as _{nickel precursor, boric acid (H 3} BO ₃ ) and potassium citrate (K ₃ (C ₆ H) as pH buffers as additives ₅ O ₇ )) each 10 g/L, sodium dodecyl sulfate (NaC ₁₂ H ₂₅ SO ₄ ) 0.02 mM as a dispersant, and sodium chloride (NaCl) 10 g/L as an electrodeposition uniformity improver were mixed to prepare a plating solution.

After putting a titanium foil as a substrate and a graphite rod as a counter electrode in the plating solution, 3 wt% of Ni is included on the titanium foil through an alloying technique using an electroplating method to apply a current of ^{20 mA/cm 2} A negative electrode was prepared by forming a zinc alloy (1 cm ^{2 ).}

Example 2: Zinc alloy containing 5 wt% Ni

Nickel precursor of nickel chloride, zinc containing (NiCl ₂₎ the Ni 5 wt% in the Example 1, the titanium foil in the same manner except that 8 g / L, instead of using 5 g / L alloy (1 cm ² ) to prepare a negative electrode by forming.

Example 3: Zinc alloy containing 10 wt% Ni

Nickel precursor of nickel chloride (NiCl ₂₎ of 5 g / L to place of 15 g / L zinc alloy and comprises a Ni 10 wt% on the titanium foil in the same manner as in Example 1 except that the used (1 cm ² ) to prepare a negative electrode by forming.

Example 4: Zinc alloy containing 10 wt% Cu

10 wt% of Cu on the titanium foil in the same manner as in Example 1, except that 15 g/L of _{copper chloride (CuCl 2} ) was used instead of using 5 g/L of nickel chloride (NiCl _{2 ), a nickel precursor.} A negative electrode was prepared by forming a zinc alloy containing (1 cm ^{2 ).}

Example 5: Zinc alloy containing 10 wt% Fe

10 wt% of Fe on the titanium foil in the same manner as in Example 1 except that 15 g/L _{of iron chloride (FeCl 2} ) was used instead of using 5 g/L of nickel chloride (NiCl _{2 ), a nickel precursor} A negative electrode was prepared by forming a zinc alloy (1 cm ^{2 ) to do.}

Comparative Example 1: Zinc

^{1 cm 2} of zinc foil was used as an anode for an aqueous zinc secondary battery.

Water-based zinc secondary battery cell

Device Example 1: Zinc alloy (3 wt% Ni) cathode was used

_{80 wt% of alpha MnO 2} as a cathode active material in N-methyl-2-pyrrolidone as a solvent, 10 wt% of polyvinylidene fluoride (PVDF) as a binder, conductive 10 wt% of Super-P was added and mixed to prepare a slurry. The slurry was coated on SUS foil and vacuum dried at 100 °C for 12 hours to prepare a positive electrode.

The negative electrode prepared according to Example 1, filter paper (100 μm filter paper), electrolyte (3 MC ₂ F ₆ O ₆ S ₂ Zn), and the positive electrode were prepared as a pouch cell to prepare an aqueous zinc secondary battery cell. prepared.

Device Example 2: Zinc alloy (5 wt% Ni) cathode was used

An aqueous zinc secondary battery cell was prepared in the same manner as in Device Example 1 except that the negative electrode prepared according to Example 2 was used instead of the negative electrode prepared according to Example 1 was used.

Device Example 3: Zinc alloy (10 wt% Ni) negative electrode

An aqueous zinc secondary battery cell was prepared in the same manner as in Device Example 1, except that the negative electrode prepared according to Example 3 was used instead of the negative electrode prepared according to Example 1 was used.

Device Example 4: Using a zinc alloy (10 wt% Cu) cathode

An aqueous zinc secondary battery cell was manufactured in the same manner as in Device Example 1, except that the negative electrode prepared according to Example 4 was used instead of the negative electrode prepared according to Example 1 was used.

Device Example 5: Use of a zinc alloy (10 wt% Fe) anode

An aqueous zinc secondary battery cell was prepared in the same manner as in Device Example 1, except that the negative electrode prepared according to Example 5 was used instead of the negative electrode prepared according to Example 1 was used.

Device Comparative Example 1: Use of Zinc Anode

An aqueous zinc secondary battery cell was prepared in the same manner as in Device Example 1, except that the negative electrode of Comparative Example 1 was used instead of the negative electrode prepared according to Example 1.

[Test Example]

Test Example 1: Life test of aqueous zinc secondary battery cell

3 shows the life test results of Device Examples 1 to 3 and Device Comparative Example 1. FIG. In detail, the aqueous zinc secondary battery cells manufactured according to Device Examples 1 to 3 and Device Comparative Example 1 exhibited capacity when charging and discharging were repeated in a voltage range of 1 to 1.8 V and an applied current of 1 A/g. will be.

Referring to FIG. 3 , it can be seen that Device Example 3 using a zinc alloy containing 10 wt% of nickel as an anode exhibits the best lifespan characteristics.

Test Example 2: Observation of anode surface after life test

4A is an SEM image of the surface of the negative electrode (Comparative Example 1) after the life test, and FIG. 4B is an SEM image of the surface of the negative electrode (Example 1) after the life test. 4C is an SEM image of the surface of the negative electrode (Example 2) after the life test, and FIG. 4D is an SEM image of the surface of the negative electrode (Example 3) after the life test.

4a to 4d, it can be confirmed that severe corrosion has occurred on the surface of Comparative Example 1, and in Example 1 containing 3 wt% of Ni, it can be confirmed that corrosion is slightly suppressed on the surface as compared to Comparative Example 1. . In Example 2 containing 5 wt% of Ni, it can be confirmed that corrosion is slightly more suppressed on the surface compared to Example 1, and in Example 3 containing 10 wt% of Ni, it can be confirmed that almost no corrosion occurs on the surface.

Therefore, when the zinc alloy containing a small amount of a heterogeneous element according to the present invention is used as an anode for an aqueous secondary battery, it can be confirmed that corrosion is suppressed in the electrolyte.

Test Example 3: Symmetric cell test

Figure 5 shows the voltage retention performance results when prepared as a symmetric cell using Example 3 as an anode and a cathode, respectively, after preparing two. _{Specifically, a symmetric cell was prepared by adding 3 M C 2} F ₆ O ₆ S ₂ Zn aqueous solution (electrolyte) to the two electrodes prepared according to Example 3, which has the best corrosion inhibition performance, as an anode and a cathode, respectively. , 1 mA/cm ² , 1 mAh/cm ^{2 The} performance was confirmed by repeating charging and discharging under the conditions.

Referring to FIG. 5 , in the symmetric cell manufactured using Example 3, it can be seen that the voltage is maintained constant when charging and discharging are repeated under the conditions of ^{1 mA/cm 2} , 1 mAh/cm ^{2 for 25 hours.} .

Test Example 4: Corrosion potential measurement

A three-electrode system using Example 3, which has the best corrosion inhibition performance, and Comparative Example 1 for comparison as a working electrode, a graphite rod as a counter electrode, Ag/AgCl as a reference electrode, and 4 wt% of NaCl aqueous solution as an electrolyte Corrosion potential was measured at scam rate of 10 mV/s, and the corrosion potential values are summarized in Table 1 below.

division Corrosion potential (mV) Comparative Example 1 -830 Example 3 -760

Referring to Table 1, since the corrosion potential of Example 3 containing the zinc alloy is higher than the corrosion potential of Comparative Example 1 containing zinc, the zinc alloy containing a small amount of heterogeneous element is used as a negative electrode in the aqueous secondary battery rather than zinc. It can be seen that the corrosion resistance is excellent when used.

test example 5: Water-based zinc of secondary battery cells life test

6 shows the life test results of Device Examples 4 and 5. In detail, the capacity (Capacity) is shown when charging and discharging the aqueous zinc secondary battery cells prepared according to Device Examples 4 and 5 at a voltage range of 1 to 1.8 V and an applied current of 1 A/g.

Referring to FIG. 6 , both Device Example 4 and Device Example 5 using a zinc alloy containing 10 wt% copper and 10 wt% iron as cathodes were zinc anodes manufactured according to Device Comparative Example 1 of FIG. 3 , respectively. It can be seen that all of the water-based zinc secondary battery cells show superior lifespan characteristics.

The scope of the present invention is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention. do.

Claims (20)

conductive substrate; and
A zinc alloy layer positioned on the conductive substrate and including zinc (Zn) and a zinc alloy having a heterogeneous element;
Anode for use in aqueous zinc secondary batteries. According to claim 1,
The zinc alloy
85 to 99% by weight of zinc; and
A negative electrode comprising: 1 to 15 wt% of a hetero element. According to claim 1,
The negative element, characterized in that it comprises at least one selected from the group consisting of nickel (Ni), copper (Cu), iron (Fe), tungsten (W) and cobalt (Co). According to claim 1,
The conductive substrate is a titanium foil, titanium foam (Ti foam), carbon nanotubes (CNT), carbon nanofiber (carbon nanofiber), carbon fiber (carbon fiber), graphene foam (graphene foam) and graphene An anode comprising at least one selected from the group consisting of fibers (graphene fiber). anode;
An anode comprising a conductive substrate and a zinc alloy layer disposed on the conductive substrate and including zinc (Zn) and a zinc alloy having a heterogeneous element;
a separator positioned between the anode and the cathode; and
water-based electrolyte;
Water-based zinc secondary battery comprising. 6. The method of claim 5,
The zinc alloy
85 to 99% by weight of zinc; And 1 to 15% by weight of heteroelements; Aqueous zinc secondary battery comprising a. 6. The method of claim 5,
The negative element, characterized in that it comprises at least one selected from the group consisting of nickel (Ni), copper (Cu), iron (Fe), tungsten (W) and cobalt (Co). 6. The method of claim 5,
The positive electrode MnO ₂ , V ₂ O ₅ , ZnMn ₂ O ₄ , ZnCo ₂ O ₄ Water-based zinc secondary battery, characterized in that it comprises at least one selected from the group consisting of metal vanadates. 6. The method of claim 5,
An aqueous zinc secondary battery, characterized in that the separator comprises at least one selected from the group consisting of filter paper, glass fiber, polyolefin, and polymer series. 6. The method of claim 5,
The aqueous electrolyte is C ₂ F ₆ O ₆ S ₂ Zn, CoSO ₄ , MnSO ₄ , Mn(CF ₃ SO ₃ ) ₂ and Na ₂ SO ₄ Water-based zinc, characterized in that it comprises at least one selected from the group consisting of secondary battery. (a) preparing a plating solution containing a zinc precursor, a heteroelement precursor and an additive; and
(b) Plating a zinc alloy layer including zinc (Zn) and a zinc alloy having a heterogeneous element on the conductive substrate by putting a conductive substrate and a counter electrode in the plating solution and applying a current to the conductive substrate and the counter electrode step to;
A method of manufacturing an anode for use in an aqueous zinc secondary battery comprising 12. The method of claim 11,
The zinc precursor is selected from the group consisting of zinc chloride (ZnCl ₂ ), zinc nitrate (Zn(NO ₃ ) ₂ ), zinc sulfate (ZnSO ₄ ), zinc acetate (Zn(CH ₃ CO ₂ ) ₂ ), and hydrates thereof. A method of manufacturing an anode, comprising at least one. 12. The method of claim 11,
The method of manufacturing a negative electrode, characterized in that the heteroelement precursor comprises at least one selected from the group consisting of a nickel precursor, a copper precursor, an iron precursor, a tungsten precursor, and a cobalt precursor. 12. The method of claim 11,
The nickel precursor is selected from the group consisting of nickel chloride (NiCl ₂ ), nickel nitrate (Ni(NO ₃ ) ₂ ), nickel sulfate (NiSO ₄ ), nickel acetate (Ni(CH ₃ CO ₂ ) ₂ ), and hydrates thereof containing one or more species;
1 selected from the group consisting of copper chloride (CuCl ₂ ), copper nitrate (Cu(NO ₃ ) ₂ ), copper sulfate (CuSO ₄ ), copper acetate (Cu(CH ₃ CO ₂ ) _{2 ), and hydrates thereof} including more than one species,
The iron precursor is iron chloride (FeCl ₂ ), iron nitrate (Fe(NO ₃ ) ₂ ), iron sulfate (FeSO ₄ ), iron acetate (Fe(CH ₃ CO ₂ ) ₂ ) and hydrates thereof 1 selected from the group consisting of including more than one species,
The tungsten precursor is sodium tungstate (Na ₂ WO ₄ ), ammonium paratungstate ((NH ₄ ) ₁₀ (H ₂ W ₁₂ O ₄₂ )), potassium tungstate (K ₂ O ₂ W), and hydrates thereof It contains one or more selected from the group,
The cobalt precursor is selected from the group consisting of cobalt chloride (CoCl ₂ ), cobalt nitrate (Co(NO ₃ ) ₂ ), cobalt sulfate (CoSO ₄ ), cobalt acetate (Co(CH ₃ CO ₂ ) ₂ ) and hydrates thereof A method of manufacturing an anode, comprising at least one. 12. The method of claim 11,
The method of manufacturing a negative electrode, characterized in that the additive comprises at least one selected from the group consisting of a pH buffering agent, a dispersing agent, and an electrodeposition uniformity improving agent. 12. The method of claim 11,
The plating solution is a method of manufacturing a negative electrode, characterized in that the sum of the concentrations of the zinc precursor and the heteroelement precursor is 10 to 150 g / L. 12. The method of claim 11,
The plating solution is a method of manufacturing a negative electrode, characterized in that the concentration of the additive is 0.1 to 200 g / L. 12. The method of claim 11,
The conductive substrate is a titanium foil, titanium foam (Ti foam), carbon nanotubes (CNT), carbon nanofiber (carbon nanofiber), carbon fiber (carbon fiber), graphene foam (graphene foam) and graphene Including at least one selected from the group consisting of fibers (graphene fiber),
The method for manufacturing a negative electrode, wherein the counter electrode comprises at least one selected from the group consisting of graphite, a graphite rod, platinum, and glassy carbon. 12. The method of claim 11,
In the step (b), the density of the current is 1 to 200 mA / cm ² Method of manufacturing a negative electrode, characterized in that. 12. The method of claim 11,
After the step (b), the method for manufacturing the negative electrode is
(c) washing and drying the zinc alloy layer plated on the conductive substrate;

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