KR20190141990A - Li/carbon cloth complex electrode and fabrication method thereof - Google Patents

Abstract

The present invention relates to a lithium metal negative electrode and a manufacturing method thereof. More particularly, the present invention relates to a lithium/carbon cloth composite electrode coated with zinc oxide (ZnO) particles and molten lithium (Li) on a carbon cloth, and a method of manufacturing the same. According to the present invention, since the lithium/carbon cloth composite electrode uses the carbon cloth having a large surface area and high electron conductivity, the lithium/carbon cloth composite electrode exhibits a relatively low current density per electrode area. Also, the lithium/carbon cloth composite electrode shows a fast electrochemical reaction rate, thereby suppressing the formation of dendrites and dead lithium and securing high life stability.

Description

Li / carbon cloth composite electrode and fabrication method thereof

The present invention relates to a lithium metal negative electrode and a method for manufacturing the same, and more particularly, a lithium / carbon fabric composite electrode coated with zinc oxide (ZnO) particles and molten lithium (Li) on a carbon cloth, and a method of manufacturing the same. It is about.

The lithium metal secondary battery is the first commercially available lithium secondary battery, using lithium metal as a negative electrode. However, the lithium metal secondary battery is due to the lithium resin phase formed on the surface of the lithium metal negative electrode, the volume expansion of the cell, the gradual decrease in capacity and energy density, short circuit due to the continuous growth of the dendrite, cycle life and cell stability problems (explosion and fire ) Has been restricted to use.

Therefore, instead of the lithium metal, a carbon-based negative electrode which is safer and can stably store lithium in a lattice or empty space has been used, and commercialization and dissemination of a full-scale lithium secondary battery is prevented due to the carbon-based negative electrode. Progressed.

To date, lithium secondary batteries have been the mainstream of carbon-based or non-carbon-based negative electrode materials. Most of the development of anode materials is focused on carbon-based (graphite, hard carbon, soft carbon, etc.) and non-carbon-based (silicon, tin, titanium oxide, etc.) materials. However, carbon-based materials have a theoretical capacity of not more than 400mAh / g, and non-carbon-based materials are more than 1000mAh / g, but have not yet solved the problems of volume expansion and performance during charging and discharging.

In addition, as the medium-large-size lithium secondary battery is recently activated, high capacity and high energy density characteristics are required, but existing materials have many limitations to meet such performance.

Recently, researches on reusing metal lithium like lithium air batteries have been actively conducted. Lithium is very light and has a potential energy capacity of over 3800mAh per gram, resulting in a very good energy density. Therefore, with the research and development of the lithium air battery, the movement to re-study the lithium metal secondary battery itself is actively progressing.

However, there are a number of problems to overcome in order to apply lithium metal as a secondary battery negative electrode material. Unlike graphite-based negative electrode materials, lithium metal anodes convert lithium in the form of ions from the anode into neutral lithium through electrochemical reactions with electrons from external conductors. It is easily formed into a dendritic shape. The non-uniform surface thus formed provides an overall expanded volume, and during discharge, lithium is more likely to dissociate directly from the lithium metal without selectively falling off from the lithium resin phase. Not only does the surface of the cathode experience very extreme volume changes, but the resulting dendrite exhibits irregular and complex morphologies. This complex aspect of the surface is not stabilized at all as the cycle progresses, resulting in a very irregular cycle life with continuous generation and decay. In addition, the lithium resin phase formed during discharge dissociates into the electrolyte region as a whole, and the resin phase continues to grow in the vertical direction, penetrating the separator and directly or indirectly contacting the anode surface located on the opposite side, thereby causing hard short or soft short. do.

In order to solve the problems of the conventional lithium metal negative electrode, the present inventors have been studying to manufacture a lithium metal negative electrode having high life stability by lowering the current density and stably maintaining the structure of the electrode during charging and discharging. It was confirmed that the lithium / carbon fabric composite electrode coated with zinc oxide (ZnO) particles and molten lithium (Li) on the fabric exhibited high stability even after 100 cycles of charge / discharge cycles, thereby completing the present invention.

1. Republic of Korea Patent Publication No. 10-2013-0067914 2. Republic of Korea Patent Publication No. 10-2013-0116403

The present invention is to solve the above problems, the first object of the present invention is to provide a lithium / carbon fabric composite electrode coated with zinc oxide (ZnO) particles and molten lithium (Li) on a carbon fabric.

It is a second object of the present invention to provide a method for producing the lithium / carbon fabric composite electrode.

It is a third object of the present invention to provide a lithium secondary battery including the lithium / carbon fabric composite electrode.

In order to achieve the first object, the present invention

Carbon Fabric,

LiZn and Li ₂ O particles formed surrounding the surface of the carbon fabric, and

Provided is a lithium / carbon fabric composite electrode including a lithium (Li) layer surrounding the carbon fabric and particles.

Also preferably, the LiZn and Li ₂ O particles may be converted by reacting zinc oxide particles with lithium, as shown in Scheme 1 below.

Scheme 1

ZnO + 3Li → LiZn + Li ₂ O

Also preferably, the LiZn and Li ₂ O particles may have a diameter of 200 nm or less.

Also preferably, the lithium / carbon fabric composite electrode may be all coated with lithium in the space between the pores and particles of the carbon fabric.

In order to achieve the second object, the present invention

(S10) forming zinc oxide (ZnO) particles on the surface of the carbon fabric; And

(S20) It provides a method of manufacturing the lithium / carbon fabric composite electrode comprising the step of contacting the carbon fabric formed with the zinc oxide particles to the molten lithium.

Also, preferably, step S10 may be performed by adding a carbon fabric to a solution in which zinc hydrate is dissolved in an organic solvent and reacting by stirring at room temperature.

Also preferably, the organic solvent may be selected from the group consisting of methanol, ethanol, propanol and isopropyl alcohol.

Also preferably, the zinc hydrate is zinc acetate hydrate, zinc nitrate hydrate (Zn (NO ₃ ) ₂ · 6H ₂ O), zinc chloride hydrate (ZnCl ₂ · 3H ₂ O) and zinc sulfate hydrate (ZnSO ₄ · 7H ₂ O) can be selected from the group consisting of.

Also preferably, the concentration of zinc hydrate in the organic solvent may be 0.05 ~ 0.1M.

Also preferably, after the step S10, the carbon fabric in which zinc oxide particles are formed may be dried at a temperature of 100 to 130 ° C. in an air atmosphere.

Also preferably, the dried carbon fabric may be further subjected to a heat treatment so that the formed zinc oxide particles are firmly attached to the carbon fabric.

Also preferably, the heat treatment may be performed at a temperature of 330 ~ 370 ℃.

Also preferably, melting of lithium in step S20 may be performed at 250 to 300 ° C. by placing a lithium foil in a crucible.

Also preferably, the S20 step may be performed under an inert gas atmosphere.

In order to achieve the third object, the present invention provides a lithium metal secondary battery including a lithium / carbon fabric composite electrode, a positive electrode, a separator interposed between the positive electrode and an electrolyte as a negative electrode.

According to the present invention, since the lithium / carbon fabric composite electrode uses a carbon fabric having a large surface area and high electron conductivity, the lithium / carbon fabric composite electrode has a relatively low current density per electrode area, and shows a fast electrochemical reaction rate. Formation of lithium is suppressed and high life stability is shown.

1 is a schematic view and a cross-sectional view of a lithium / carbon fabric composite electrode according to an embodiment of the present invention.
2 is a flowchart illustrating a method of manufacturing a lithium / carbon fabric composite electrode according to an embodiment of the present invention.
Figure 3 is a photograph showing a state in which molten lithium is coated on the carbon fabric when manufacturing a lithium / carbon fabric composite electrode according to an embodiment of the present invention.
4 is a scanning electron microscope (SEM) photograph of a carbon fabric before and after coating according to an embodiment of the present invention ((a) carbon fabric, (b) ZnO coated carbon fabric, (c) ZnO and Li coated carbon) textile).
5 is a scanning electron microscope (SEM) photograph showing a cross section of a lithium / carbon fabric composite electrode prepared according to an embodiment of the present invention.
6 is an XRD analysis graph of a lithium / carbon fabric composite electrode manufactured according to an embodiment of the present invention.
Figure 7 is a graph showing the stability of life when applying a current at a constant current density in a symmetric cell of a lithium / carbon fabric composite electrode or a general lithium metal electrode prepared according to an embodiment of the present invention ((a) 1 mA / cm ² ).
Figure 8 is a graph showing the stability of the life when applying a current at a constant current density in a symmetric cell of a lithium / carbon fabric composite electrode or a general lithium metal electrode prepared according to an embodiment of the present invention (b) 5 mA / cm ² ).
Figure 9 is a graph showing the stability of life when applying a current at a constant current density in a symmetric cell of a lithium / carbon fabric composite electrode or a general lithium metal electrode prepared according to an embodiment of the present invention ((c) 10 mA / cm ² ).
FIG. 10 is a graph showing discharge capacity and coulombic efficiency in a lithium / carbon fabric composite electrode prepared in accordance with an embodiment of the present invention, or a battery in which a general lithium metal is used as a negative electrode and an LCO as a positive electrode.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

While the invention allows for various modifications and variations, specific embodiments thereof are illustrated by way of example in the drawings and will be described in detail below. However, it is not intended to be exhaustive or to limit the invention to the precise forms disclosed, but rather the invention includes all modifications, equivalents, and alternatives consistent with the spirit of the invention as defined by the claims.

1 is a schematic diagram of a lithium / carbon fabric composite electrode according to an embodiment of the present invention.

Referring to FIG. 1, the lithium / carbon fabric composite electrode according to the present invention may include a carbon fabric 10, particles 20 including LiZn and Li ₂ O, and a lithium (Li) layer 30. have.

In the lithium / carbon fabric composite electrode according to the present invention, the carbon fabric 10 serves as a support of the composite electrode, and since pores are formed between the fibers to increase the surface area, the lithium metal per electrode It reduces the current density, thereby inhibiting the formation of dendrites and dead rithium during charging and discharging of lithium metal.

In addition, since the carbon fabric 10 exhibits high electron conductivity, the carbon fabric 10 may exhibit a faster electrochemical reaction rate than when lithium metal is used alone.

The carbon fabric 10 may be formed of a carbon fiber fabric as shown in Figure 4 (a), but is not limited thereto, the carbon fiber itself may be used.

In the lithium / carbon fabric composite electrode according to the present invention, particles 20 including LiZn (21) and Li ₂ O (22) are formed on the surface of the carbon fabric (10).

The particles 20 are converted by reacting zinc oxide (ZnO) particles with the molten lithium metal 30 as shown in Scheme 1 below, and after preparing the lithium / carbon fabric composite electrode through XRD analysis It can be seen (see Fig. 6).

Scheme 1

ZnO + 3Li → LiZn + Li ₂ O

The particles 20 may be formed by hydrothermal synthesis, the size of which may be 200 nm or less, but is not limited thereto.

In the lithium / carbon fabric composite electrode according to the present invention, the lithium layer 30 includes the carbon fabric 10 and the LiZn (21) and Li ₂ O (22) formed on the surface of the carbon fabric (10) It is formed in a shape surrounding the particles 20. The lithium layer 30 is coated with molten lithium metal as it permeates the carbon fabric, and thus the space between the pores and the particles 20 of the carbon fabric 10 is coated with lithium.

The present invention also provides a method for producing the lithium / carbon fabric composite electrode.

2 is a flowchart illustrating a method of manufacturing a lithium / carbon fabric composite electrode according to an embodiment of the present invention.

2, the method of manufacturing a lithium / carbon fabric composite electrode according to the invention

(S10) forming zinc oxide (ZnO) particles on the surface of the carbon fabric; And

(S20) comprising the step of contacting the carbon fabric formed with the zinc oxide particles to the molten lithium.

First, step S10 is to form zinc oxide (ZnO) particles on the surface of the carbon fabric.

In the production of the lithium / carbon fabric composite electrode according to the present invention, in order to coat lithium on a carbon fabric, it is preferable to first form a zinc oxide having a high affinity with lithium on the carbon fabric. The zinc oxide particles may be formed using hydrothermal synthesis.

Specifically, zinc oxide particles may be formed on the surface of the carbon fabric by adding a carbon fabric to a solution in which zinc hydrate is dissolved in an organic solvent and stirring the mixture at room temperature. In this case, the organic solvent used may be methanol, ethanol, propanol, isopropyl alcohol and the like, but is not limited thereto.

As the zinc hydrate, zinc acetate hydrate, zinc nitrate hydrate (Zn (NO ₃ ) ₂ · 6H ₂ O), zinc chloride hydrate (ZnCl ₂ · 3H ₂ O), zinc sulfate hydrate (ZnSO ₄ · 7H ₂ O), etc. can be used. May be, but is not limited thereto.

The concentration of zinc hydrate relative to the organic solvent is preferably 0.05 to 0.1 M.

The stirring is performed so that zinc oxide particles are uniformly formed on the carbon fabric. The stirring may be performed using a magnetic bar or the like, and may be performed for 3 to 7 hours.

Thereafter, the carbon fabric on which the zinc oxide particles are formed may be dried at an air atmosphere at a temperature of 100 to 130 ° C., and the dried carbon fabric may further be heat-treated so that the formed zinc oxide particles are firmly attached to the carbon fabric. can do. The heat treatment is preferably carried out at a temperature of 330 ~ 370 ℃ bar, if the heat treatment temperature is less than 330 ℃ may include impurities such as organic matter, if it exceeds 370 ℃ carbon on the carbon fabric may be oxidized.

Next, step S20 is a step of contacting the carbon fabric formed with the zinc oxide particles to the molten lithium.

Lithium metal has a high affinity for zinc oxide. Accordingly, when the zinc oxide particles coated carbon fabric is contacted with the molten lithium, as shown in FIG. 3, the molten lithium penetrates the carbon fabric as if the water soaks in the sponge, and the lithium is uniformly distributed throughout the carbon fabric. Coated.

Melting of the lithium may be carried out at 250 ~ 300 ℃ put a lithium foil in the crucible. If the temperature of the crucible exceeds 300 ° C., there is a risk of denaturation of lithium.

Since the lithium is easily oxidized in the air, it is preferable to perform the lithium coating in an inert gas such as argon gas atmosphere. In one embodiment of the present invention, lithium coating was performed under an argon gas atmosphere in a glove box.

Since the fabricated lithium / carbon fabric composite electrode uses a carbon fabric having a large surface area and high electron conductivity, the lithium / carbon fabric composite electrode has a relatively low current density per electrode area and exhibits a fast electrochemical reaction rate, thereby forming dendrite and deadly lithium. It is suppressed and shows high lifetime stability.

In addition, the present invention provides a lithium metal secondary battery comprising a lithium / carbon fabric composite electrode, a positive electrode, a separator interposed between the positive electrode and the electrolyte prepared as described above as a negative electrode.

The lithium metal secondary battery may be manufactured according to a conventional method known in the art. For example, a lithium metal secondary battery may be assembled by interposing a separator between the positive electrodes, and then, an electrolyte may be added to the assembly. Prepared by injection.

The positive electrode to be applied together with the above-described negative electrode is not particularly limited, but may have a form in which the positive electrode layer is bound on the current collector.

At this time, the manufacturing method of the positive electrode in detail, the positive electrode material containing a positive electrode active material, optionally a conductive material and / or a binder and the like dispersed in a solvent or a dispersion medium, for example N-methylpyrrolidone (NMP) After the slurry is prepared, the prepared slurry may be coated on a positive electrode current collector, subjected to a heat treatment, and then pressed.

In this case, the cathode layer may be a conventional cathode active material that may be used for the cathode of a conventional lithium metal secondary battery. Non-limiting examples of positive electrode active materials that can be used include olivine (LiFePO ₄ ), nanoparticle olivine (LiFePO ₄ ) coated with carbon particles, lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ) and lithium manganese oxide Lithium-containing metal complex oxide selected from the group consisting of (LiMn ₂ O ₄ ), a mixture of the lithium-containing metal complex oxide, a solid solution of the lithium-containing metal complex oxide, or aluminum, iron, copper, titanium, magnesium Substituted materials can be used as the positive electrode active material.

In addition, non-limiting examples of the conductive material can be selected from the group consisting of graphite, hard carbon, soft carbon, carbon fiber, carbon nanotubes, carbon black, acetylene black, Ketjen black and Lonza carbon.

Non-limiting examples of the binder include polyvinylidene fluoride, copolymers of vinylidene fluoride and hexafluoropropylene, polyvinyl chloride, polyvinyl alcohol, polyvinylacetate, ethylvinylacetate, carboxymethylcellulose, styrene / Butadiene rubber / carboxymethylcellulose or mixtures of one or more thereof. In this case, the use ratio of the positive electrode active material, the conductive material and the binder constituting the positive electrode layer may be used within a range generally used in this field, preferably in a weight ratio of 8: 1: 1 to 9.8: 0.1: 0.1. Can be.

In the lithium metal secondary battery according to the present invention, the separator may be a polyethylene-based single membrane or a multilayer membrane of polyethylene and polypropylene. Preferred separator thickness may range from 16 to 25 μm, but is not particularly limited thereto.

In the lithium metal secondary battery according to the present invention, the electrolyte may be in a form in which a lithium salt is dissolved or dissociated in an organic solvent.

Non-limiting examples of organic solvents that can be used include ethylene carbonate, propylene carbonate, dibeta carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, methylformate, Ethylformate, gamma-butyrolactone, or mixtures of one or more thereof.

In addition, non-limiting examples of lithium salts that can be used include lithium perchlorate (LiClO ₄ ), lithium triflate (LiCF ₃ SO ₃ ), lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium Trifluoromethanesulfonylimide (LiN (CF ₃ SO ₂ ) ₂ ) or a mixture of one or more thereof. The concentration of lithium salt in the electrolyte is preferably 1 to 1.5M.

Hereinafter, preferred examples are provided to aid the understanding of the present invention. However, the following preparation examples are merely to aid the understanding of the present invention, and the present invention is not limited by the following preparation examples.

< Production Example  1> lithium / Carbon fabric  Fabrication of Composite Electrodes

The carbon fabric was washed twice with water and ethanol to remove impurities on the carbon fabric. Next, zinc acetate dihydrate was dissolved in methanol to prepare a 0.08 M solution.

The washed carbon fabric was added to the prepared zinc acetate dihydrate solution, and stirred for 5 hours using a magnetic bar for uniform synthesis. Thereafter, the carbon fabric was taken out and dried at 110 ° C. in an air atmosphere. The dried carbon fabric was heat-treated at 350 ° C. for 5 hours in air to prepare a zinc oxide coated carbon fabric.

Next, the lithium foil is placed in a crucible and melted at 300 ° C., and then the zinc oxide coated carbon fabric is brought into contact with molten lithium in an argon (Ag) atmosphere in a glove box, and the molten lithium metal is deposited on the carbon fabric. A lithium / carbon fabric composite electrode coated with lithium as a whole was prepared.

The prepared lithium / carbon fabric composite electrode was observed with a scanning electron microscope and shown in FIGS. 4 and 5.

4 is a scanning electron microscope (SEM) photograph of a carbon fabric before and after coating according to an embodiment of the present invention ((a) carbon fabric, (b) ZnO coated carbon fabric, (c) ZnO and Li coated carbon) textile).

As shown in Figure 4, (a) ZnO-coated carbon fabric itself consists of a smooth fiber, (b) ZnO-coated carbon fabric does not show a difference as before coating when expanded to 200 times, but expanded to 10000 times It was confirmed that ZnO particles were formed on the fiber surface of the carbon fabric. (c) In the case of the carbon fabric coated with ZnO and lithium, it was confirmed that a lithium film was formed on the carbon fabric fiber at 200 times magnification, and particles were formed on the surface of the carbon fiber at 10000 times magnification.

5 is a scanning electron microscope (SEM) photograph showing a cross section of a lithium / carbon fabric composite electrode prepared according to an embodiment of the present invention.

As shown in FIG. 5, when the cross section of the manufactured lithium / carbon fabric composite electrode was examined, it was confirmed that a lithium film was formed around the circular carbon fiber.

In addition, X-ray diffraction analysis of the prepared lithium / carbon fabric composite electrode is shown in Figure 6 the results.

As shown in FIG. 6, when zinc oxide was coated on the carbon fabric, a peak of zinc oxide was observed during X-ray diffraction analysis. However, when zinc oxide and lithium were coated on the carbon fabric, no zinc oxide peak was observed. Peaks of LiZn and Li ₂ O were observed. It can be seen from this that zinc oxide (ZnO) is converted to LiZn and Li ₂ O by reacting with lithium.

< Production Example  2> lithium / Carbon fabric  Fabrication of lithium metal secondary battery (symmetric cell) including composite electrode

The lithium / carbon fabric composite electrode prepared in Preparation Example 1 was applied to both the cathode and the anode, and a 2032 coin cell was constructed using a separator and an electrolyte. The separator was used as a PE separator, the electrolyte was used EC / EMC = 1/2 (v / v) (EC: ethylene carbonate, EMC: ethyl methyl carbonate) containing 1.0M LiPF ₆ .

The constant current life characteristics test of the manufactured lithium metal secondary battery was carried out and shown in FIGS. 7 to 9. For comparison, a regular lithium metal electrode symmetric battery was also tested for constant current life characteristics.

7 to 9 are graphs showing lifetime stability when a current is applied at a constant current density in a symmetric battery of a lithium / carbon fabric composite electrode or a general lithium metal electrode manufactured according to an embodiment of the present invention. In this case, the results obtained by setting the current density to 1 mA / cm ² , 5 mA / cm ² , and 10 mA / cm ² are shown in FIGS. 7, 8, and 9, respectively.

As shown in Figures 7 to 9, in the case of a symmetric battery using lithium metal as an electrode, the resistance increases as time increases, but the magnitude of the applied voltage also increases, but the lithium / carbon fabric composite according to the present invention In the case of the electrode, it was found that the voltage remained almost constant over time, indicating a high lifetime stability.

Therefore, the lithium metal secondary battery including the lithium / carbon fabric composite electrode according to the present invention exhibits high life stability, and thus may be usefully used instead of the existing lithium metal secondary battery.

< Production Example  3> lithium / Carbon fabric  Fabrication of a lithium full cell including a composite electrode

A lithium metal secondary cell was manufactured in the same manner as in Preparation Example 2, except that the lithium / carbon fabric composite electrode prepared in Preparation Example 1 was used as a cathode, and a lithium cobalt oxide (LiCoO ₂ ) cathode was used. .

The change in discharge capacity and the coulombic efficiency according to the cycle of the manufactured lithium metal secondary battery were measured and shown in FIG. 10. For comparison, a test on a lithium metal secondary battery using general lithium metal as a negative electrode was also performed.

FIG. 10 is a graph showing discharge capacity and coulombic efficiency in a lithium / carbon fabric composite electrode prepared in accordance with an embodiment of the present invention, or a battery in which a general lithium metal is used as a negative electrode and an LCO as a positive electrode.

As shown in FIG. 10, the secondary battery using a general lithium metal as a negative electrode showed a sharp decrease in discharge capacity when charging and discharging more than 70 cycles, and the coulomb efficiency also decreased as the number of cycles increased.

However, in the secondary battery using the lithium / carbon fabric composite electrode according to the present invention as a negative electrode, the discharge capacity was kept constant even after 100 cycles of charge and discharge, and the coulombic efficiency was also maintained at 98%.

Therefore, it can be seen that the lithium metal secondary battery including the lithium / carbon fabric composite electrode according to the present invention can significantly improve cycle life characteristics of the battery without chemical damage.

Although the present invention has been described above with reference to preferred embodiments, it should be understood that the present invention is not limited to the above embodiments. The present invention can be variously modified and modified within the scope of the following claims, which are all within the scope of the invention. Accordingly, the invention is limited only by the claims and the equivalents thereof.

10: carbon fabric
20: particles comprising LiZn and Li ₂ O
21: LiZn
22: Li ₂ O
30: lithium (Li)

Claims (15)

Carbon Fabric,
LiZn and Li ₂ O particles formed surrounding the surface of the carbon fabric, and
A lithium (Li) layer surrounding the carbon fabric and particles
Lithium / carbon fabric composite electrode.
The method of claim 1,
The LiZn and Li ₂ O particles are lithium / carbon fabric composite electrode, characterized in that the zinc oxide particles are converted by reacting with lithium, as shown in Scheme 1 below.
Scheme 1
ZnO + 3Li → LiZn + Li ₂ O
The method of claim 1,
The LiZn and Li ₂ O particles are lithium / carbon composite electrode, characterized in that the diameter is 200 nm or less.
The method of claim 1,
The lithium / carbon fabric composite electrode is lithium / carbon fabric composite electrode, characterized in that all the space between the pores and particles of the carbon fabric is coated with lithium.
(S10) forming zinc oxide (ZnO) particles on the surface of the carbon fabric; And
(S20) comprising the step of contacting the carbon fabric formed with the zinc oxide particles in the molten lithium,
A method of manufacturing the lithium / carbon fabric composite electrode of claim 1.
The method of claim 5,
Step S10 is a method for producing a lithium / carbon fabric composite electrode characterized in that the zinc hydrate is added to the carbon fabric in a solution dissolved in an organic solvent and stirred at room temperature to react to form zinc oxide particles on the surface of the carbon fabric.
The method of claim 6,
The organic solvent is a method for producing a lithium / carbon fabric composite electrode, characterized in that selected from the group consisting of methanol, ethanol, propanol and isopropyl alcohol.
The method of claim 6,
The zinc hydrate is a group consisting of zinc acetate hydrate, zinc nitrate hydrate (Zn (NO ₃ ) ₂ · 6H ₂ O), zinc chloride hydrate (ZnCl ₂ · 3H ₂ O), and zinc sulfate hydrate (ZnSO ₄ · 7H ₂ O) Method for producing a lithium / carbon fabric composite electrode, characterized in that selected from.
The method of claim 6,
The concentration of zinc hydrate in the organic solvent is a method of manufacturing a lithium / carbon fabric composite electrode, characterized in that 0.05 ~ 0.1M.
The method of claim 5,
After the step S10, the carbon fabric formed with zinc oxide particles is a method of manufacturing a lithium / carbon fabric composite electrode, characterized in that the drying at a temperature of 100 ~ 130 ℃ in the air atmosphere.
The method of claim 10,
The dried carbon fabric is a method of manufacturing a lithium / carbon fabric composite electrode, characterized in that further performing a heat treatment so that the formed zinc oxide particles are firmly attached to the carbon fabric.
The method of claim 11,
The heat treatment is a method of manufacturing a lithium / carbon fabric composite electrode, characterized in that performed at a temperature of 330 ~ 370 ℃.
The method of claim 5,
Melting of lithium in step S20 is a method of manufacturing a lithium / carbon fabric composite electrode, characterized in that the lithium foil in the crucible is carried out at 250 ~ 300 ℃.
The method of claim 5,
Step S20 is a method of manufacturing a lithium / carbon fabric composite electrode, characterized in that carried out under an inert gas atmosphere.
A lithium metal secondary battery comprising a lithium / carbon fabric composite electrode of claim 1, a positive electrode, a separator interposed between the positive electrode, and an electrolyte as a negative electrode.

Images