KR20150130175A - High energy metal secondary battery and system using the same - Google Patents

Abstract

The present invention relates to a metal secondary battery and a system using the same. Provided is the metal secondary battery which includes a negative electrode which includes a negative electrode collector and includes a metal, a metal alloy, or a metal intercalation compound located on the negative electrode collector; a positive electrode collector; a solid electrolyte; and an electrolyte. The electrolyte is located between the negative electrode and the solid electrolyte. One side of the solid electrolyte is in contact with the electrolyte. A catalyst is located on the surface of the other side of the solid electrolyte. The positive electrode collector is electrically connected to the solid electrolyte on which the catalyst is located.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal secondary battery,

A metal secondary battery, and a system using the same.

Lithium-ion batteries are becoming one of the three most advanced components in the information electronics industry, along with semiconductors and display devices. In recent years, lithium ion batteries have been used not only in portable communication devices such as mobile phones and personal digital assistants (PDA) but also in electric vehicles, and it is therefore essential to increase the capacity, miniaturization and weight of the batteries.

However, as the battery becomes smaller and lighter, the storage capacity for charging and discharging becomes smaller. Therefore, it is required to develop a battery having improved charge-discharge storage capacity for use without supplying external power for a long period of time.

For example, a lithium-air battery is a battery in which lithium (Li) metal is used as a cathode and oxygen (O ₂ ) in the air is used as an anode, and a new energy storage It is means.

The lithium-air battery is a battery system in which a secondary battery and a fuel cell technology are combined. In the cathode, lithium oxidation / reduction reaction occurs, and at the anode, reduction / oxidation reaction of oxygen introduced from the outside occurs. The theoretical energy density of the lithium-air battery is 11,140 Wh / kg, which is very high compared to other secondary batteries.

This type of lithium-air battery consists of a charge / discharge system in which the reactants are stored according to the oxidation reaction of lithium generated in the anode, and then reused during charging.

Storage of the lithium oxide in the anode for the structure of the charge and discharge battery may cause problems such as the capacity and the rate characteristic of the battery.

Therefore, a structure of a lithium secondary battery having a new structure is required.

A metal secondary battery, and a system using the same.

According to an embodiment of the present invention, there is provided a negative electrode comprising a negative electrode collector and a metal metal, a metal alloy, or a metal intercalation compound disposed on the negative electrode collector; Anode collector; Solid electrolytes; And an electrolyte, wherein the electrolyte is positioned between the cathode and the solid electrolyte, one surface of the solid electrolyte is in contact with the electrolyte, the other surface of the solid electrolyte has a catalyst on its surface, and the solid electrolyte side And the positive electrode collector are electrically connected to each other.

In the metal secondary battery, the cathode active material may not exist on the cathode current collector.

The metal secondary battery may discharge all the metal ions in the negative electrode to the outside of the battery upon discharge.

The metal secondary battery may be in the form of obtaining metal ions from a separate external device upon charging.

The external device may include a solution containing a metal, and may be a structure in which a solution containing the metal is electrically coupled to a side of the solid electrolyte where the catalyst is located.

The solution containing the metal may be brine, seawater, a metal solution recovered from the spent battery, or a combination thereof.

The solid electrolyte may include an amorphous ion conductive material, a Na superionic conductor (NASICON), a sodium sulfide based solid electrolyte, a sodium oxide based solid electrolyte, or a combination thereof.

The electrolyte is a liquid electrolyte, and may include a solvent and a lithium salt.

The solvent may be at least one selected from the group consisting of propylene carbonate, ethylene carbonate, fluoroethylene carbonate, diethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, Examples of the solvent include lactone, dioxolane, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, Examples of the organic solvent include dimethyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, dibutyl carbonate, diethylene glycol, dimethyl ether, dimethyldiglycol, dimethyltriglycol, Dimethyl tetraglycol, or a combination thereof.

Wherein the lithium salt is selected from the group consisting of LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , i (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ , LiN (C _x F _{2x + 1} SO ₂ ) (C _y F _{2y + 1} SO ₂ ) where x and y are natural numbers, LiCl, LiI, or a combination thereof.

According to another embodiment of the present invention, there is provided a negative electrode comprising a negative electrode collector and a negative electrode portion including a metal metal, a metal alloy, or a metal intercalation compound disposed on the negative electrode collector; A positive electrode portion including a positive electrode collector; Solid electrolytes; And an electrolyte portion, wherein the electrolyte portion is located between the cathode and the solid electrolyte, one surface of the solid electrolyte is in contact with the electrolyte portion, the other surface of the solid electrolyte has a catalyst located on its surface, And the positive electrode current collector is electrically connected to the negative electrode and metal ions in the negative electrode portion are passed through the electrolyte portion and discharged to the outside of the battery through the catalyst on the surface of the solid electrolyte. .

The metal secondary battery system may include a separate metal supply unit outside the battery.

The metal supply unit is electrically connected to the solid electrolyte side where the catalyst is located, and can supply metal ions to the cathode unit through external energy.

The external energy may be solar, wind, tidal, thermal, nuclear, or a combination thereof.

The metal supply portion may include a solution containing a metal, and the solution containing the metal may be a salt solution, a seawater, a metal solution recovered from a spent battery, or a combination thereof.

The solid electrolyte may include an amorphous ion conductive material, a Na superionic conductor (NASICON), a sodium sulfide based solid electrolyte, a sodium oxide based solid electrolyte, or a combination thereof.

The electrolyte portion includes a liquid electrolyte, which may include a solvent and a lithium salt.

The solvent may be at least one selected from the group consisting of propylene carbonate, ethylene carbonate, fluoroethylene carbonate, diethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, Examples of the solvent include lactone, dioxolane, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, Examples of the organic solvent include dimethyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, dibutyl carbonate, diethylene glycol, dimethyl ether, dimethyldiglycol, dimethyltriglycol, Dimethyl tetraglycol, or a combination thereof.

Wherein the lithium salt is selected from the group consisting of LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , i (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ , LiN (C _x F _{2x + 1} SO ₂ ) (C _y F _{2y + 1} SO ₂ ) where x and y are natural numbers, LiCl, LiI, or a combination thereof.

The metal secondary battery system may be used in an unmanned robot system.

A metal secondary battery having a novel structure and a system thereof can be provided. As a result, it is possible to realize a large-capacity secondary battery having excellent characteristics in a small electronic apparatus.

1 is a configuration diagram of a metal secondary battery according to an embodiment of the present invention.
FIG. 2 is a configuration diagram of a metal secondary battery according to an embodiment of the present invention.
3 is charge / discharge data of a secondary battery according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

According to an embodiment of the present invention, there is provided a negative electrode comprising a negative electrode collector and a metal metal, a metal alloy, or a metal intercalation compound disposed on the negative electrode collector; Anode collector; Solid electrolytes; And an electrolyte, wherein the electrolyte is positioned between the cathode and the solid electrolyte, one surface of the solid electrolyte is in contact with the electrolyte, the other surface of the solid electrolyte has a catalyst on its surface, and the solid electrolyte side And the positive electrode collector are electrically connected to each other.

The metal secondary battery according to an embodiment of the present invention may be a metal-air battery (for example, oxidizing metal to discharge air), metal-water (for example, Ion may be flowed in a solvent. More specifically, the structure is not limited as long as it has a structure that effectively discharges metal ions in the cathode through the catalyst to generate electricity.

The metal secondary battery according to an embodiment of the present invention may have a structure in which the cathode active material does not exist on the cathode current collector. That is, the metal ion moved from the cathode may not be separately stored during the discharge.

More specifically, the metal secondary battery may discharge all the metal ions in the negative electrode to the outside of the battery upon discharge.

At this time, the metal secondary battery can obtain metal ions from a separate external device upon charging. That is, when the metal is discharged, there is no separate cathode active material, which is similar to a light type primary battery. However, when the battery is charged, the secondary battery has a structure similar to that of a conventional secondary battery.

For example, the external device may include a solution containing a metal, and a structure in which a solution containing the metal and a solid electrolyte side on which the catalyst is disposed are electrically coupled.

In this way, the metal in the external device moves toward the cathode so that the battery can be charged.

The solution containing the metal may be saline, seawater, a lithium solution recovered from the spent battery, or a combination thereof. However, the present invention is not limited thereto.

More specifically, a system using such a battery will be described.

According to another embodiment of the present invention, there is provided a negative electrode comprising a negative electrode collector and a negative electrode portion including a metal metal, a metal alloy, or a metal intercalation compound disposed on the negative electrode collector; A positive electrode portion including a positive electrode collector; Solid electrolytes; And an electrolyte portion, wherein the electrolyte portion is located between the cathode and the solid electrolyte, one surface of the solid electrolyte is in contact with the electrolyte portion, the other surface of the solid electrolyte has a catalyst located on its surface, And the cathode current collector is electrically connected to the cathode current collector and the metal ion in the cathode part is passed through the electrolyte part and discharged to the outside of the battery through the catalyst on the surface of the solid electrolyte. .

This is a system in which a metal is not separately stored in an anode portion as in the case of a primary battery during discharging and a separate metal is supplied from a metal supplying portion to be described later when charging, as in the above-described embodiment of the present invention.

More specifically, the metal secondary battery system may include a separate lithium supply unit outside the battery.

The metal supply unit is electrically connected to the solid electrolyte side where the catalyst is located, and can supply metal ions to the cathode unit through external energy. That is, the system may have this type of charging structure.

At this time, the external energy may be solar energy, wind force, assist force, thermal power, nuclear power, or a combination thereof, but is not limited thereto.

The metal supply portion may include a solution containing a metal, and the solution containing the metal may be a salt solution, a seawater, a metal solution recovered from a spent battery, or a combination thereof. However, the present invention is not limited thereto.

The metal secondary battery includes: a positive electrode collector; A negative electrode made of a metal metal, a metal alloy, or a metal intercalation compound; A solid electrolyte separating the positive electrode and the negative electrode; And an electrolyte.

A method of manufacturing such a metal secondary battery will be briefly described below.

First, the positive electrode collector is prepared. The cathode current collector may be a metal thin film such as carbon paper, carbon fiber, carbon cloth, carbon felt, aluminum, copper, or a combination thereof.

At this time, no separate cathode active material is required.

Next, a negative electrode is prepared by using an active material such as a metal metal, a metal alloy, or a metal intercalation compound commonly used in the related art. Next, a solid electrolyte impregnated with an electrolyte is disposed between the positive electrode collector and the negative electrode plate to form a battery structure.

The solid electrolyte may be an amorphous ion conductive material such as a phosphorus-based glass, an oxide / sulfide based glass, a Na superionic conductor (NASICON), a sodium sulfide based solid electrolyte, a sodium oxide based solid electrolyte, And combinations of these. However, the present invention is not limited thereto.

The electrolytic solution may include a solvent and a lithium salt. Examples of the solvent include propylene carbonate, ethylene carbonate, fluoroethylene carbonate, diethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, butylene carbonate, benzonitrile, acetonitrile, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, 1,2-dimethoxyethane, Dimethyl carbonate, dimethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, dibutyl carbonate, diethyl carbonate, diethyl carbonate, Ethylene glycol, dimethyl ether, dimethyldiglycol, dimethyltriglycol, dimethyltetra And in the glycol, and the like can be used, the lithium salt is _{LiPF 6, LiBF 4, LiSbF 6} , LiAsF 6, LiClO 4, LiCF 3 SO 3, i (CF 3 SO 2) 2 N, LiC 4 F 9 SO 3, LiSbF 6 , LiAlO ₄ , LiAlCl ₄ , LiN (C _x F _{2 x +1} SO ₂ ) (C _y F _{2y + 1} SO ₂ ) (where x and y are natural numbers), LiCl, LiI or combinations thereof .

The lithium secondary battery is suitable for applications requiring a high capacity such as an electric vehicle, a mobile phone, a portable computer, and the like, and can be widely used in a hybrid vehicle or the like in combination with a conventional internal combustion engine, a fuel cell and a supercapacitor. .

In addition, it can be used in systems such as micro-unmanned aerial vehicles, miniature unmanned submarines and the like, which are becoming a recent issue.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.

Example

Manufacture of anode

Carbon paper (Fuel Cell Store, 2050-A) was used as a current collector. The anode collector was filled with seawater, and the collector was impregnated with seawater to prepare a cathode.

The porosity of the carbon paper is 28 mu m.

Cathode manufacturing

Stainless steel (McMASTER) was used as a collector.

After the organic electrolyte in the negative electrode container was charged, the prepared negative electrode was impregnated.

The organic electrolyte was ethylene carbonate (EC): was prepared by mixing: (volume ratio 1: 1) and 1M NaClO ₄ of the sodium salt (Aldrich), diethylene carbonate (DEC).

Solid electrolyte  Produce

NASICON-type Li _{1 .3} Ti _{1 .7} Al _{0 .3} (PO ₄ ) ₃ was used as a solid electrolyte. The solid electrolyte was prepared by a solid-state reaction in this laboratory. The solid phase reaction well known in the art will omit specific methods.

And a solid electrolyte was positioned between the anode portion and the cathode portion. The thickness of the solid electrolyte is 1 mm.

Manufacture of batteries

The negative electrode portion contained the negative electrode collector and the organic electrolyte, and the negative electrode portion was completely sealed with the solid electrolyte. The cathode and the organic electrolyte are completely blocked physically from the cathode material and are stable, and only the metal ion can migrate through the solid electrolyte. Polymer epoxy is used to seal the solid electrolyte to the cathode, and various epoxy resins available in the market can be used.

Experimental Example

Evaluation of battery characteristics

3 is charge / discharge data of a secondary battery according to an embodiment of the present invention.

It can be seen from FIG. 3 that lithium ions dissolved in water are accumulated in the stainless steel on the cathode by charging lithium ion aqueous solution. The accumulated lithium ions are discharged to water again while producing electricity when the battery is discharged. The charge voltage is about 3.7 V and the discharge voltage is about 3.2 V on the average. In the first cycle, an irreversible capacity of about 50% appeared, indicating the amount consumed in the formation of a solid electrolyte interface (SEI) on the cathode surface when lithium ions were initially formed on the cathode. After SEI formation, stable reversible capacity is shown.

Similar results are obtained when lithium is charged in an aqueous solution and then discharged in air.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (20)

A negative electrode including a negative electrode current collector and a metal metal, a metal alloy, or a metal intercalation compound disposed on the negative electrode current collector;
Anode collector;
Solid electrolytes; And
Comprising an electrolyte,
Wherein the electrolyte is disposed between the cathode and the solid electrolyte, one surface of the solid electrolyte is in contact with the electrolyte, the other surface of the solid electrolyte has a catalyst on its surface,
Wherein the solid electrolyte side where the catalyst is located and the positive electrode collector are electrically connected to each other.
The method according to claim 1,
Wherein the metal secondary battery has no positive electrode active material on the positive electrode collector.
The method according to claim 1,
Wherein the metal secondary battery discharges all the metal ions in the negative electrode to the outside of the battery upon discharge.
The method according to claim 1,
Wherein the metal secondary battery is in a form to obtain metal ions from a separate external device upon charging.
5. The method of claim 4,
The external device includes:
Wherein the solution containing the metal is a structure in which the solution containing the metal and the solid electrolyte side on which the catalyst is placed are electrically coupled.
6. The method of claim 5,
Wherein the metal-containing solution is a salt solution, seawater, a metal solution recovered from a spent battery, or a combination thereof.
The method according to claim 1,
Wherein the solid electrolyte comprises an amorphous ion conductive material, a Na superionic conductor (NASICON), a sodium sulfide based solid electrolyte, a sodium oxide based solid electrolyte, or a combination thereof.
The method according to claim 1,
Wherein the electrolyte is a liquid electrolyte, and comprises a solvent and a lithium salt.
9. The method of claim 8,
The solvent may be at least one selected from the group consisting of propylene carbonate, ethylene carbonate, fluoroethylene carbonate, diethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, Examples of the solvent include lactone, dioxolane, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, Examples of the organic solvent include dimethyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, dibutyl carbonate, diethylene glycol, dimethyl ether, dimethyldiglycol, dimethyltriglycol, Dimethyl tetraglycol, or a combination thereof.
9. The method of claim 8,
Wherein the lithium salt is selected from the group consisting of LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , i (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ , _{LiN (C x F 2x +1 SO} 2) (C y F 2y +1 SO 2) ( stage x, y are natural numbers), LiCl, LiI, or a lithium secondary battery that is a combination thereof.
A negative electrode including a negative electrode current collector and a metal metal, a metal alloy, or a metal intercalation compound disposed on the negative electrode current collector;
A positive electrode portion including a positive electrode collector;
Solid electrolytes; And
And an electrolyte portion,
Wherein the electrolyte portion is located between the cathode and the solid electrolyte, one surface of the solid electrolyte is in contact with the electrolyte portion, the other surface of the solid electrolyte has a catalyst on its surface,
The solid electrolyte side where the catalyst is located and the cathode current collector are electrically connected,
Wherein the metal ions in the cathode section pass through the electrolyte section and are discharged to the outside of the battery through the catalyst on the surface of the solid electrolyte.
12. The method of claim 11,
Wherein the metal secondary battery system includes a separate metal supply unit outside the battery.
13. The method of claim 12,
Wherein the metal supply unit is electrically connected to the solid electrolyte side on which the catalyst is located to supply metal ions to the cathode unit through external energy.
14. The method of claim 13,
Wherein the external energy is solar energy, wind, assist, thermal, nuclear, or a combination thereof.
14. The method of claim 13,
Wherein the metal supply part comprises a solution containing a metal, and the solution containing the metal is a salt solution, seawater, a metal solution recovered from a spent battery, or a combination thereof.
12. The method of claim 11,
Wherein the solid electrolyte comprises an amorphous ion conductive material, a Na superionic conductor (NASICON), a sodium sulfide based solid electrolyte, a sodium oxide based solid electrolyte, or a combination thereof.
12. The method of claim 11,
Wherein the electrolyte portion comprises a liquid electrolyte, which comprises a solvent and a lithium salt.
18. The method of claim 17,
The solvent may be at least one selected from the group consisting of propylene carbonate, ethylene carbonate, fluoroethylene carbonate, diethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, Examples of the solvent include lactone, dioxolane, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, Examples of the organic solvent include dimethyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, dibutyl carbonate, diethylene glycol, dimethyl ether, dimethyldiglycol, dimethyltriglycol, Dimethyl tetraglycol, or a combination thereof.
8. The method of claim 7,
Wherein the lithium salt is selected from the group consisting of LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , i (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ , _{LiN (C x F 2x +1 SO} 2) (C y F 2y +1 SO 2) ( stage x, y is a natural number), the lithium secondary battery system, LiCl, LiI, or to a combination thereof.
12. The method of claim 11,
Wherein the metal secondary battery system is used in an unmanned robot system.

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