WO2018190559A1 - Electroplating solution for lithium metal, and method for manufacturing lithium metal electrode by using same - Google Patents

Abstract

The present invention relates to an electroplating solution for a lithium metal, and a method for manufacturing a lithium metal electrode by using the same and, more specifically, a lithium metal electrode is manufactured using electroplating, wherein the lithium metal electrode having improved surface characteristics can be manufactured by electroplating using a plating solution comprising lithium nitride and a metal nitride, and the lifespan characteristics of a battery can be improved by applying the lithium metal electrode to the battery.

Description

Electroplating solution for lithium metal and manufacturing method of lithium metal electrode using same

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0048299 dated April 14, 2017 and Korean Patent Application No. 10-2018-0038063 dated April 2, 2018. All content disclosed in the literature is included as part of this specification.

The present invention relates to an electroplating solution for lithium metal and a method for producing a high capacity lithium metal electrode using the same.

Recently, the development of the electronic industry enables the miniaturization and lightening of electronic equipment, and thus the use of portable electronic devices is increasing. The need for a secondary battery having a high energy density as a power source for such a portable electronic device has been increasing, and research on lithium secondary batteries has been actively conducted.

Representative high capacity batteries of lithium secondary batteries include lithium sulfur batteries, lithium air batteries, and the like, and they commonly use lithium metal as a high capacity negative electrode material.

Lithium metal is an ideal material as a cathode of a high energy density lithium secondary battery with a high theoretical capacity of 3862 mAh / g and a low standard electrode potential (-3.04 vs SHE). However, due to the deterioration of safety due to the internal short circuit of the battery due to lithium dendrite growth, there is a problem when commercializing as a negative electrode material of the lithium battery.

In addition, when the lithium ions are reduced on the surface of the lithium metal, irreversible may be generated by forming a solid electrolyte interphase (SEI) layer according to a combination of a solvent and a salt of the electrolyte.

When the SEI layer is unstable, the direct reaction between the electrolyte and the lithium metal continuously occurs, thereby causing additional irreversibility, which may cause a decrease in the charge and discharge efficiency of the lithium metal. In addition, the electrolyte may be depleted due to the consumption of the electrolyte used in generating the SEI layer, and the life of the battery may be reduced by the gas generated as a by-product.

Therefore, when manufacturing an electrode using lithium metal, it is necessary to develop a technology for a lithium metal manufacturing method to control the surface shape of the lithium metal to ensure safety.

[Preceding technical literature]

[Patent Documents]

Korean Patent No. 0447792, "Li-electrode using porous three-dimensional current collector, manufacturing method and lithium battery"

The inventors of the present invention have conducted various researches to solve the above problems. As a result, the lithium metal electrode was manufactured by electroplating, and the lithium metal electrode with controlled surface properties was manufactured by changing the composition of the plating solution used during electroplating. It was confirmed that the lithium metal electrode manufactured by the method described above exhibited flat surface characteristics, thereby improving the life characteristics of the battery.

Accordingly, an object of the present invention is to provide an electroplating solution for lithium metal capable of producing a lithium metal electrode.

Still another object of the present invention is to provide a method of manufacturing a high capacity lithium metal electrode.

In order to achieve the above object, the present invention is an electroplating solution for lithium metal, the plating solution is an ether solvent; Lithium salts; Lithium nitrate; And it provides an electroplating solution for lithium metal containing an additive represented by the formula (1).

<Formula 1>

MNO _X

In Formula 1, M is Cs, Rb, K, Ba, Sr, Ca, Na or Mg, and x is 2 or 3.

The plating solution may use at least one selected from the group consisting of lithium salt, lithium ingot and transition metal oxide as a source of lithium metal.

The lithium salt may be included in a concentration of 1 M to 7 M.

The lithium nitrate may be included in 1 to 5% by weight.

Concentration ratio ([Li ⁺ ] / [M ⁺ ]) of Li ⁺ of the lithium nitrate and M ⁺ of the additive represented by Formula 1 may be 10 or more.

The ether solvent may be at least one selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl ether and dibutyl ether.

The lithium salt is LiFSI, LiPF ₆ , LiCl, LiBr, LiI, LiClO ₄ , LiBF ₄ , LiB ₁₀ Cl ₁₀ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiAsF ₆ , LiSbF ₆ , LiPF ₆ , LiAlCl ₄ , CH ₃ SO ₃ Li, CF ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, may be one or more selected from the group consisting of one or more selected from the group consisting of lithium chloroborane and lithium 4-phenyl borate.

The lithium nitrate may be at least one selected from the group consisting of lithium nitrate (LiNO ₃ ) and lithium nitrite (LiNO ₂ ).

The additive is selected from the group consisting of potassium nitrate (KNO ₃ ), cesium nitrate (CsNO ₃ ), magnesium nitrate (MgNO ₃ ), barium nitrate (BaNO ₃ ), potassium nitrite (KNO ₂ ) and cesium nitrite (CsNO ₂ ). It may be one or more.

The lithium nitrate and the additive may be lithium nitrate (LiNO ₃ ) and cesium nitrate (CsNO ₃ ), respectively.

The present invention also relates to a method of manufacturing a lithium metal electrode using electroplating, the method of manufacturing a lithium metal electrode electroplating lithium metal on a current collector using the plating solution.

The method of manufacturing a lithium metal electrode includes: (a) immersing a source of lithium metal and a current collector to be electroplated with lithium metal in the plating solution; And (b) electroplating lithium metal on the current collector by applying a reduction potential to the plating solution.

The source of the lithium metal may be at least one selected from the group consisting of lithium salts, lithium ingots and transition metal oxides.

The current collector may be selected from the group consisting of Cu, Al, Ni, Fe, SUS (steel use stainless) and Ti, and may be in the form of a three-dimensional structure.

The electroplating solution for lithium metal according to the present invention is used for the electroplating of lithium metal, and using at least one selected from the group consisting of lithium salt, lithium ingot and transition metal oxide as a source of lithium metal among electroplating. By being used for the electroplating process, the surface characteristics of the lithium metal electrode manufactured according to the composition of the plating solution can be controlled.

In addition, a plating solution containing lithium nitrate (LiNO ₃ ) and cesium nitrate (CsNO ₃ ) at a predetermined concentration during electroplating and a thin film lithium having smooth surface characteristics during the electroplating process using the lithium metal source. A metal electrode can be manufactured.

In addition, it is possible to manufacture a lithium metal electrode having a thickness of 20㎛ or less level by the conventional rolling method.

In addition, a lithium metal electrode can be manufactured using various current collectors, such as Cu, Al, Ni, Fe, SUS, and Ti, which have been difficult to use by conventional rolling methods.

1 is a schematic diagram of a lithium half battery capable of electroplating according to an embodiment of the present invention.

2 is a schematic view showing a lithium source according to an embodiment of the present invention.

3 is a SEM (Scanning Electron Microscope) photograph of the surface of the lithium metal electrode prepared in Examples 1 to 4 and Comparative Examples 1 to 4, respectively.

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

Electroplating solution for lithium metal

The present invention relates to an electroplating solution for lithium metal, ether solvent; Lithium salts; Lithium nitrate; And an additive represented by Formula 1 below.

<Formula 1>

MNO _X

In Formula 1, M is Cs, Rb, K, Ba, Sr, Ca, Na or Mg, and x is 2 or 3.

The plating solution of the present invention is used for the electroplating of lithium metal, in particular lithium salt (Li Salt), lithium ingot and transition metal oxide as a source of lithium metal during electroplating One or more selected from the group consisting of may be used for the use for the electroplating, if the compound that can provide a lithium ion is not limited thereto (FIG. 2).

In the present invention, the lithium salt is LiPF ₆ , LiClO ₄ , LiAsF ₆ , LiBF ₄ , LiSbF ₆ , LiAl0 ₄ , LiAlCl ₄ , LiCF ₃ SO ₃ , LiC ₄ F9SO ₃ , LiN (C ₂ F ₅ SO ₃ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ . LiN (CaF _{2a + 1} SO ₂ ) (CbF _{2b + 1} SO ₂ ), provided that a and b are natural numbers, preferably ₁ ≦ a ≦ 20 _{and 1} ≦ b ≦ 20, LiCl, LiI and LiB ( C ₂ O ₄ ) ₂ may be one or more selected from the group consisting of.

The transition metal oxide is LiM'O ₂ (M 'is Co, Ni or Mn), Li _{1 + x} Mn _{2 - x} O ₄ ⁺ (0≤x≤0.3) and LiNi _{1 - x} M _x O ₂ (M May be Co, Mn, Al, Cu, Fe, Mg, B, or Ga, and 0.01 ≦ x ≦ 0.3). For example, the lithium metal oxide may be LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , Li (Ni _a Mn _b Co _c ) O ₂ (a + b + c = 1), LiNi _{0 . 5} Mn _{1 . 5} O ₄ or LiNi _0.5 Mn _0.5 O ₂ .

In the present invention, the ether solvent is a non-aqueous solvent for forming an ether plating solution, tetrahydrofuran (THF), 2-methyltetrahydrofuran (MTHF), dimethyl ether (DME) and dibutyl ether ( DBE) may be one or more selected from the group consisting of, in particular, when using dimethyl ether (DME) may be advantageous for electroplating lithium metal on the current collector.

In the present invention, the lithium salt is LiFSI, LiPF ₆ , LiCl, LiBr, LiI, LiClO ₄ , LiBF ₄ , LiB ₁₀ Cl ₁₀ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiAsF ₆ , LiSbF ₆ , 1 selected from the group consisting of at least one selected from the group consisting of LiPF ₆ , LiAlCl ₄ , CH ₃ SO ₃ Li, CF ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, chloroborane lithium and lithium 4-phenyl borate It may be more than one species, and in particular, when using LiFSI may be advantageous for electroplating lithium metal on the current collector.

In addition, the concentration of the lithium salt may be appropriately adjusted according to the composition of the plating solution, for example, may be 1.0 M to 7.0 M, preferably 1 M to 4 M. If the lithium salt is less than 1.0 M, the conductivity of the plating solution may not be good, and thus the high rate discharge characteristics and lifetime characteristics may be reduced. Can be degraded.

In the present invention, the plating solution may form a stable film on the lithium metal electrode by the lithium nitrate and the additive represented by the formula (1) having a NO bond in the molecule, thereby, side reaction of the lithium metal and the plating solution As this is suppressed, the stability of the lithium metal electrode and the plating solution is further improved, and the life of the battery can be greatly improved.

For example, the lithium nitrate may be at least one selected from the group consisting of lithium nitrate (LiNO ₃ ) and lithium nitrite (LiNO ₂ ), and the additive may be potassium nitrate (KNO ₃ ), cesium nitrate (CsNO ₃ ), It may be at least one selected from the group consisting of magnesium nitrate (MgNO ₃ ), barium nitrate (BaNO ₃ ), potassium nitrite (KNO ₂ ) and cesium nitrite (CsNO ₂ ).

The lithium nitrate may be included in an amount of 1 to 5 wt% based on the total weight of the plating solution represented by Formula 1, and when the content of the additive is less than 1 wt%, the amount of product (Li _x NO _y ) is excessively small. As a protective layer, there is a problem that the thickness is not sufficient, and when it is more than 5% by weight, there may be a problem such as deterioration of efficiency due to excessive consumption of lithium as an active material when the protective layer is generated.

In the plating solution, the amount of the lithium nitrate and the additive represented by the formula (1) is a concentration ratio of Li ⁺ derived from the lithium nitrate and the M ⁺ derived from the additive represented by the formula (1) ([Li ⁺ ] / [M ⁺ ] Can be defined as

The concentration ratio ([Li ⁺ ] / [M ⁺ ]) may be 10 or more. When the concentration ratio is less than the above range, M + may be reduced without being present in an ionic state, and thus, lithium dendrite inhibitory effect may be insignificant, and surface planarization may be difficult. Preferably the concentration ratio (Li ⁺ ] / [M ⁺ ]) may be 10 to 40.

In particular, the plating solution may be advantageous to planarize the surface of the lithium metal electrode when lithium nitrate and additives include lithium nitrate (LiNO ₃ ) and cesium nitrate (CsNO ₃ ), respectively.

When cesium nitrate (CsNO ₃ ) is included as the additive, the concentration in the plating solution may be 0.1 M or less per Li ⁺ 1M. For example, the reduction potential of Cs ⁺ ions changes according to the concentration. When the concentration of Cs ⁺ per 1M Li ⁺ is more than 0.1M, the Cs ⁺ ions become higher than the reduction potential of Li ⁺ ions. Reduced before ⁺ ions. Since Cs ⁺ must be present on the surface in the ionic state, it is possible to inhibit dendrite as a leveler. Therefore, the concentration of Cs ⁺ per 1M of Li ⁺ ions may be 0.1M or less, preferably, Cs ⁺ 0.03 to 0.07 per 1M of Li ^+. Can be M.

Method of manufacturing lithium metal electrode

The present invention also relates to a method for manufacturing a lithium metal electrode using electroplating, the method of manufacturing a lithium metal electrode characterized in that the surface of the lithium metal electrode produced according to the composition of the plating solution used during the electroplating is controlled. It is about.

According to one embodiment of the present invention, electroplating may be performed using a lithium half battery.

1 is a schematic diagram of a half cell that can be electroplated according to an embodiment of the present invention.

Referring to FIG. 1, the upper surface of the upper lithium metal 40 of the Cu current collector 10 is used by using a Cu current collector 10 as a cathode, a source of lithium metal 20 as an anode, and an ether plating solution 30. By plating, a lithium metal electrode may be manufactured.

At this time, the specific conditions of the electroplating is C-rate 0.01 to 0.5 C, it may be to use a current with a current density of 0.1 to 5 mAh / ㎠, if out of the conditions of such electroplating, when electroplating lithium metal The surface characteristics of the formed lithium metal electrode may be degraded. That is, a problem may arise such that the surface of the lithium metal electrode is not electroplated flat or the thickness of the electroplating becomes thick.

The ether-based plating solution 30 is the same as the electroplating solution for lithium metal as described above.

The source of lithium metal 20 is also as described above.

In the present invention, the current collector capable of electroplating lithium metal may be selected from the group consisting of Cu, Al, Ni, Fe, SUS (steel use stainless) and Ti, the current collector may be in the form of a three-dimensional structure have.

Such a current collector could not be used in a rolling process used in lithium metal in the prior art, and there is an advantage in that various current collectors can be used by electroplating using an ether plating solution.

The lithium metal electrode manufactured by the electroplating method as described above may have a flatter surface due to reduced surface roughness. When using a lithium metal electrode having a flat surface, it is possible to prevent the lithium growth generated during charging and discharging to grow into a needle shape that causes internal short circuits, thereby improving battery driving safety.

In addition, it is easy to control the thickness of the lithium metal to be plated by electroplating the lithium metal directly on the current collector. Therefore, lithium metal can be electroplated to a thin thickness which cannot be manufactured by the conventional rolling process, and finally, a lithium metal electrode having a thickness of 20 μm or less can be produced by rolling.

In addition, it is also possible to control the shape of the lithium dendrites formed on the surface of the lithium metal electrode according to the composition of the ether-based plating solution used during the electroplating. When lithium dendrites are needle-shaped, lithium dendrites easily fall out of the electrode and lose their electrical conductivity, increasing the probability of dead lithiation, leading to reduced efficiency. In addition, in the case of needle type, it may cause a short-circuit through the separator and cause a fire due to excessive heat.

In this way, by changing the composition of the ether-based plating solution to control the surface characteristics of the lithium metal electrode, for example, roughness, degree of flattening, thickness, the shape of the lithium dendrites can improve the life characteristics of the battery to which the lithium metal electrode is applied. .

Hereinafter, preferred examples are provided to help the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. It goes without saying that changes and modifications belong to the appended claims.

In Examples 1 to 4 and Comparative Examples 1 to 4, the lithium metal is plated on the Cu current collector by electroplating, and the composition of the plating solution used during the electroplating is changed as shown in Table 1 below. Prepared.

	Plating solution
	menstruum	Lithium salt	Lithium nitrate	additive	Concentration ratio Note 1) ([Li + ] / [M + ])
Example 1	DME	LiFSI (3M)	LiNO 3 (2 wt.%)	CsNO 3 (0.15M)	20
Example 2	DME	LiFSI (1M)	LiNO 3 (2 wt.%)	CsNO 3 (0.15M)	20
Example 3	DME	LiFSI (3M)	LiNO 3 (2 wt.%)	CsNO 3 (0.05M)	60
Example 4	DME	LiFSI (3M)	LiNO 3 (2 wt.%)	CsNO 3 (0.3M)	10
Comparative Example 1	EC: DEC: DMC	LiPF 6 (1M)	-	VC (2% by weight)	-
Comparative Example 2	DME	LiFSI (1M)	LiNO 3 (2 wt.%)	-	-
Comparative Example 3	DME	LiFSI (3M)	LiNO 3 (2 wt.%)	-	-
Comparative Example 4	DME	LiFSI (3M)	-	CsNO 3 (0.15M)	-

Note 1) Concentration ratio ([Li ⁺ ] / [M ⁺ ]) means the concentration ratio of Li ⁺ of lithium nitrate and Cs ⁺ of additive.

Example 1

A lithium metal electrode was prepared by plating lithium metal on a Cu current collector by electroplating.

At this time, the plating solution is dissolved in LiFSI lithium salt in dimethyl ether (DME) ether solvent to be 3M, and then added so that the lithium nitrate LiNO ₃ is 2% by weight based on the total weight of the plating solution. the LiNO ₃ was used as the plating solution was prepared such that the Li ⁺ and derived additive CsNO ₃ Cs ⁺ concentration ratio ^{([Li +] / [Cs} +]) 20 of the origin (Table 1).

Further, C-rate 0.2 C (using a Cu current collector as a negative electrode and using a lithium half battery including a positive electrode containing LiCoO ₂ as a lithium source, a polyethylene separator disposed between the positive electrode and the negative electrode and the plating solution) 0.95 mA) and 3 mA / cm <2> of electric current, and electroplating was performed.

Example 2

A lithium metal electrode was prepared in the same manner as in Example 1 except that electrolytic plating was performed by dissolving LiFSI, which is a lithium salt, to 1 M.

Example 3

Performed using a plating solution preparation, but the first embodiment in the same way as in the Li ⁺ and additives of CsNO ₃ derived Cs ⁺ concentration ratio ^{([Li +] / [Cs} +]) of the LiNO ₃ derived such that the 60 lithium electrode Was prepared.

Example 4

Performed using a plating solution preparation, but the first embodiment in the same way as in the Li ⁺ and additives of CsNO ₃ derived Cs ⁺ concentration ratio ^{([Li +] / [Cs} +]) of the LiNO ₃ derived such that the 10 lithium electrode Was prepared.

Comparative Example 1

The same procedure as in Example 1 was carried out, except that the plating solution was dissolved in LiPF 6, which is a lithium salt, in a carbonate solvent of EC: DEC: DMC (25:50:25 v / v) as shown in Table 1. After this, a lithium metal electrode was manufactured using a plating solution in which VC (vinyl carbonate) was dissolved by 2% by weight based on the total plating solution weight. In this case, EC is ethylene carbonate, DEC is diethlyene carbonate, and DMC is dimethylene carbonate.

Comparative Example 2

The same procedure as in Example 1 was carried out except that the plating solution was dissolved in LiFSI, which is a lithium salt, in dimethyl ether (DME), an ether solvent, to 1 M, and LiNO _{3, which} was a lithium nitrate, was By adding 2% by weight, using a plating solution prepared without using an additive, a lithium metal electrode was prepared.

Comparative Example 3

The same procedure as in Example 1 was carried out except that the plating solution was dissolved in LiFSI, which is a lithium salt, in dimethyl ether (DME), an ether solvent, to 2 M, and LiNO _{3, which} was a lithium nitrate, was By adding 2% by weight, using a plating solution prepared without using an additive, a lithium metal electrode was prepared.

Comparative Example 4

The same procedure as in Example 1 was carried out except that the plating solution was dissolved in LiFSI, which is a lithium salt, in dimethyl ether (DME), an ether solvent, to 3 M, and LiNO _{3, which} was a lithium nitrate, was A lithium metal electrode was prepared using a plating solution prepared by adding CsNO ₃ as an additive to 0.15 M without using it.

Experimental Example 1 Comparison of Surface Properties of Lithium Metal Electrode

The surface characteristics of the lithium metal electrodes prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were observed.

3 is a SEM (Scanning Electron Microscope) photograph of the surface of the lithium metal electrode prepared in Examples 1 to 4 and Comparative Examples 1 to 4, respectively.

Referring to FIG. 3, it can be seen that the surface of the lithium metal electrode prepared in Example 1 has a relatively flat surface.

From this, it can be seen that the surface characteristics of the lithium metal electrode electroplated using the plating solution containing LiNO ₃ and CsNO ₃ together.

In Examples 1 to Referring to 4, LiNO ₃ and CsNO even with a plating solution containing ₃ together, the LiNO of Li ^+, and additives of the _three derived CsNO ₃ derived Cs ⁺ in the concentration ratio ([Li ^+] / [ It can be seen that the surface properties of the lithium metal electrode vary depending on Cs ⁺ ]).

For example, when the concentration ratio ([Li ⁺ ] / [Cs ⁺ ]) is relatively high as in Example 3, it can be seen that the surface characteristics of the lithium metal electrode are somewhat reduced.

In addition, among Comparative Examples 1 to 4, Comparative Example 1 using a carbonate solvent had the best surface flatness and lithium dendrite was observed in the acicular form.

If the lithium dendrites are needle-shaped, the lithium dendrites easily fall out of the electrode and lose their electrical conductivity, which increases the probability of dead lithiation, leading to reduced efficiency. In addition, when lithium dendrite is acicular, it may cause a problem such as causing a short-circuit through a separator and causing a fire due to excessive heat. Therefore, when the dendrite grows flat, the efficiency of lithium metal can be increased by reducing the probability of the dendrite falling out of the electrode and losing its function as an active material, and the safety can be greatly improved by preventing the short circuit occurring when the membrane is destroyed. .

Although the present invention has been described above by means of limited embodiments and drawings, the present invention is not limited thereto, and the technical concept of the present invention and the following will be described by those skilled in the art to which the present invention pertains. Various modifications and variations are possible without departing from the scope of the appended claims.

[Description of the code]

1: lithium half cell

10: whole house

20: lithium source

30: ether plating solution

40: lithium metal

Claims (15)

1. As electroplating solution for lithium metal,

   The plating solution is an ether solvent; Lithium salts; Lithium nitrate; And an additive represented by the following Chemical Formula 1; an electroplating solution for lithium metal comprising:

   <Formula 1>

   MNO _X

   In Formula 1, M is Cs, Rb, K, Ba, Sr, Ca, Na or Mg, and x is 2 or 3.
2. The method of claim 1,

   The plating solution is a lithium metal electroplating solution using at least one selected from the group consisting of lithium salt, lithium ingot and transition metal oxide as a source of lithium metal.
3. The method of claim 1,

   The lithium salt is an electroplating solution for lithium metal contained in a concentration of 1 M to 7 M.
4. The method of claim 1,

   The lithium nitrate is 1 to 5% by weight electroplating solution for lithium metal.
5. The method of claim 1,

   The concentration ratio ([Li ⁺ ] / [M ⁺ ]) of Li ⁺ of the lithium nitrate and M ⁺ of the additive represented by Chemical Formula 1 is 10 or more.
6. The method of claim 1,

   The ether solvent is at least one selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl ether and dibutyl ether electroplating solution for lithium metal.
7. The method of claim 1,

   The lithium salt is LiFSI, LiPF ₆ , LiCl, LiBr, LiI, LiClO ₄ , LiBF ₄ , LiB ₁₀ Cl ₁₀ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiAsF ₆ , LiSbF ₆ , LiPF ₆ , LiAlCl ₄ An electroplating solution for lithium metal, which is at least one selected from the group consisting of CH ₃ SO ₃ Li, CF ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, chloroborane lithium, and lithium 4-phenyl borate.
8. The method of claim 1,

   The lithium nitrate is at least one selected from the group consisting of lithium nitrate (LiNO ₃ ) and lithium nitrite (LiNO ₂ ) electroplating solution for lithium metal.
9. The method of claim 1,

   The additive is selected from the group consisting of potassium nitrate (KNO ₃ ), cesium nitrate (CsNO ₃ ), magnesium nitrate (MgNO ₃ ), barium nitrate (BaNO ₃ ), potassium nitrite (KNO ₂ ) and cesium nitrite (CsNO ₂ ). Electroplating solution for lithium metal of at least one kind.
10. The method of claim 1,

    The lithium nitrate and additives are lithium nitrate (LiNO ₃ ) and cesium nitrate (CsNO ₃ ), respectively, electroplating solution for lithium metal.
11. As a method of manufacturing a lithium metal electrode using electroplating,

    A method of manufacturing a lithium metal electrode, wherein the metal is electroplated on a current collector using the plating solution of any one of claims 1 to 10.
12. The method of claim 11,

    (a) immersing a source of lithium metal and a current collector to be electroplated with lithium metal in the plating solution; And

    (b) electroplating lithium metal on the current collector;

    Method for producing a lithium metal electrode comprising a.
13. The method of claim 11,

    The lithium metal source is a method of producing a lithium metal electrode of at least one selected from the group consisting of lithium salts, lithium ingots and transition metal oxides.
14. The method of claim 11,

    The current collector is a method of manufacturing a lithium metal electrode of at least one selected from the group consisting of Cu, Al, Ni, Fe, SUS (steel use stainless) and Ti.
15. The method of claim 11,

    The current collector is a method of manufacturing a lithium metal electrode in the form of a three-dimensional structure.

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