KR101219462B1 - Negative Electrode of Hybrid Capacitors and Hybrid Capacitor Using The Same - Google Patents

Abstract

Hybrid electrode for an electrode according to the present invention-a current collector plate; It includes an activated carbon layer formed on the current collector plate and a material layer that can utilize the operation mechanism of the lithium ion battery.

Description

Negative Electrode of Hybrid Capacitors and Hybrid Capacitor Using The Same}

The present invention relates to a hybrid capacitor.

Electric Double Layer Capacitors (EDLC) and Hybrid Capacitors (EDLC) with capacitances of tens to hundreds of Farads (F) compared to conventional capacitors with capacitances of several microfarads (μF, micro-Farad). Capacitor) has been commercialized.

In general, an electric double layer capacitor charges and discharges electrical energy by a mechanism using physical adsorption and desorption of ions on the surface of activated carbon by forming the -electrode and the + electrode with the same material. It is formed of material and uses the operation mechanism of the electric double layer capacitor using the electric double layer at the -electrode, and the different mechanism at each electrode by using the mixing mechanism of the operation mechanism of the lithium ion battery at the + electrode. The hybrid capacitor has a larger capacitance and a higher energy density than the electric double layer capacitor, but has a low operating voltage characteristic, and thus the hybrid capacitor has a narrower range than the electric double layer capacitor.

The present invention is to solve the above-mentioned problems of the prior art, it is one of the main objectives of the present invention to provide a structure of a cathode for a hybrid capacitor having a high operating voltage characteristics.

Hybrid electrode for an electrode according to the present invention-a current collector plate; It includes an activated carbon layer formed on the current collector plate and a material layer that can utilize the operation mechanism of the lithium ion battery.

In one example, the material layer capable of utilizing the operation mechanism of the lithium ion battery is a 3d metal oxide layer.

In one example, the formula of the 3d transition metal oxide is represented by M'xM''yO4, and M'x and M''y are chromium (Chrome, Cr), manganese (Mn), and cobalt (Cobalt, Co, respectively). ), One of different materials selected from nickel (Ni, Ni) and copper (Copper, Cu).

In one example, the material layer that can utilize the operation mechanism of the lithium ion battery is a tin oxide-based material.

In one example, the tin oxide-based material is at least one of tin oxide (SnO 2), staannous pyrophosphate (Sn 2 P 2 O 7), SnPBO 6, and SnPO 4 Cl.

In one example, the material layer capable of utilizing the operation mechanism of the lithium ion battery is a tin based alloy layer.

In one example, the tin-based alloy layer, tin-iron (Iron, Fe) alloys, tin-cobalt alloys, tin-manganese alloys, tin- vanadium (Vandium, V) alloys, tin-titanium (Titianium, Ti) alloys At least one of them.

In one example, the material layer that can utilize the operation mechanism of the lithium ion battery is a lithium metal nitride (Lithium Metal Nitride) layer.

In one example, the lithium metal nitride layer is at least one of lithium molybdenum nitride (LiMoN 2) and lithium tungsten nitride (LiWN 2).

In one example, the material layer capable of utilizing the operation mechanism of the lithium ion battery includes at least one of soft carbon, hard carbon, and carbon black.

In one example, the material layer that can utilize the operation mechanism of the lithium ion battery is a lithium-based metal layer.

In one example, the lithium-based metal layer, Li22Sb, Li22Sn5, Li22Pb-based materials including Li22Pb5, Li22Si5, LiAl-based materials, LiC-based materials including LiC and LiC6, and Li any one or more.

In one example, the material layer that can utilize the operating mechanism of the activated carbon layer and the lithium ion battery formed on the current collector plate, a material layer that can utilize the operation mechanism of the lithium ion battery is formed on one surface of the current collector plate, An activated carbon layer is formed in the.

In one example, the material layer and the activated carbon layer that can utilize the operation mechanism of the lithium ion battery is formed to a thickness of 50 to 300 μm.

In one example, a material layer and an activated carbon layer capable of utilizing the operation mechanism of the lithium ion battery are formed on one side and the other side of the current collector plate.

In one example, the material layer and the activated carbon layer capable of utilizing the operation mechanism of the lithium ion battery are rolled and formed on the current collector plate.

Hybrid capacitor according to the present invention + electrode; Electrolyte; And a -electrode including a current collector plate, a material layer capable of utilizing an operation mechanism of a lithium ion battery formed on the current collector plate, and activated carbon.

In one example, the + electrode, the current collector; And at least one layer of lithium metal oxide and lithium metal phosphate formed on the current collector plate.

In one embodiment, the material layer that can utilize the operation mechanism of the lithium ion battery formed on the current collector plate, 3d metal oxide layer (3d metal oxide) layer, tin oxide-based material layer, tin-based alloy (Tin) a carbon material layer including at least one of a based alloy layer, a lithium metal nitride layer, a soft carbon, a hard carbon, and carbon black, and At least any one of the lithium-based metal layer.

According to the present invention, an improved operating voltage range can be obtained by using a material capable of utilizing the operating mechanism of activated carbon and a lithium ion battery as a -electrode of a hybrid capacitor. Furthermore, it is provided with the advantages of both the fast operation speed and high instantaneous power, which are advantages of the electric double layer capacitor, and the high energy density of the lithium ion battery.

1 is a view for explaining the operation of the hybrid capacitor.
FIG. 2 is a schematic diagram illustrating an operating voltage range of a conventional hybrid capacitor, and FIG. 3 is a schematic diagram illustrating an operating voltage range of a hybrid capacitor according to the present invention.
4 and 5 are schematic diagrams for explaining a method of forming a negative electrode of a hybrid capacitor according to the present invention.

Advantages and features of the present invention, and methods for achieving them will be apparent with reference to the embodiments described below in detail with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be embodied in various different forms, and the present embodiments only make the disclosure of the present invention complete, and are common in the art to which the present invention pertains. It is provided to fully inform those skilled in the art of the scope of the invention, which is to be defined only by the scope of the claims. Like reference numerals refer to like elements throughout.

The hybrid capacitor 10 has an asymmetric electrode structure in which the -electrode 100 material and the + electrode 200 material are formed of different materials. The operation of the supercapacitor having such an asymmetric electrode structure will be described with reference to FIG. 1. The supercapacitor acts as a mixing mechanism of the operation mechanism of the lithium ion battery and the operation mechanism of the electric double layer capacitor. A lithium ion battery uses energy by intercalation, which is a phenomenon in which lithium ions in a lithium metal oxide electrode are interposed between molecules of a + electrode or a -electrode material, and deintercalation, which is an extraction phenomenon. Store or release it.

In contrast, an electric double layer in an electric double layer capacitor refers to a double layer made of dipoles in which positive and negative charges are continuously distributed on the one side and the other side in the thin film layer of the object, respectively, with the same surface density. In the electrode 100, an electric double layer is formed at the interface between the electrode surface and the electrolyte (100 on the left side of FIG. 1), and uses electrical power to store electrical energy and to desorb (100 on the right side of FIG. 1) to release energy. In the + electrode 200, lithium ions move from the − electrode to the + electrode through the intercalation (200 on the left side of FIG. 1) and the deintercalation (200 on the right side of FIG. 1) as described above. It stores and moves energy from + electrode to-electrode to release energy.

In the hybrid capacitor, the positive electrode 200 is lithium cobalt oxide (LiCoO 2), lithium manganese oxide (LiMn 2 O 4), or lithium nickel oxide (Lithium Nickel Oxide), which is a material used for a lithium ion battery. LiNiO2), Lithium Iron Phostphate (LiFePO4), Lithium Flouride Iron Phostphate (Li2FePO4F), LiCo1 / 3Ni1 / 3Mn1 / 3O2, Li (LiaNixMnyCoz) O2 and the like are formed on the current collector plate. .

Lithium salts such as lithium fluorophosphate (Lithium Fluorophosphate, LiPF4), Lithium Fluoroborate (LiBF4), Lithium Perchlorate (LiClO4), etc. are used as electrolytes in order to use the mechanism of the lithium ion battery. Organic solvents such as ethylene carbonate (C 3 H 4 O 3), dimethyl carbonate (dimethyl carbonate, C 3 H 6 O 3), or diethyl carbonate (C 5 H 10 O 3) are used.

In order to use the mechanism of the electric double layer capacitor, an aqueous solution or an organic electrolyte is used, and considering that the pore size of the activated carbon used for the negative electrode is approximately 2 nm, excellent charge and discharge characteristics and high capacity can be obtained only when the salt size is appropriate. . In one example, tetraalkylammonium salts such as tetraethylammonium Tetrafluoroborate (C8H20NBF4) are used by dissolving propylene carbonate (C4H6O3) or acetonitrile (CH3CN) as an electrolyte. In another example, the electrolyte may be a solute made of pyrrolidinium salts such as butyl methyl pyrrolidinium, ethyn methyl pyrrolidinium, and dimethyl pyrrolidinium. Mixed with a solvent containing at least one of propylene carbonate (Propylene Carbonate), ethylene carbonate (Ethylene Carbonate), dimethyl carbonate (Dimethyl Carbonate), diethyl carbonate (Diethyl Carbonate), and ethyl methyl carbonate (Ethyl Methyl Carbonate) use. In another example, the electrolyte is a solute made of pyrrolidinium salts such as butylmethylpyrrolidinium, ethynmethylpyrrolidinium and dimethylpyrrolidinium, and tetraethylammonium tetrafluoroborate and ethylmethylimidazolium tetrafluoro. Solute mixed with ammonium salts such as borate, tetraethylammonium hexafluoroborate, tetraethylammonium perchlorate and the like is added to a solvent containing at least one of propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate. Use by mixing. Since the asymmetric electrode capacitor according to the present invention uses both the mechanism of the lithium ion battery and the mechanism of the electric double layer capacitor as described above, the electrolyte of the above-described lithium ion battery and the electrolyte of the electric double layer capacitor are mixed and used.

In the electrode 100 of the hybrid capacitor according to the present invention, in order to use the operation mechanism of the electric double layer capacitor, a material capable of utilizing the operation mechanism of activated carbon and lithium ions is formed on the current collector plate. Therefore, in the -electrode, the energy is charged and discharged by electrostatic adsorption and desorption using activated carbon, and in addition to the activated carbon, the operation mechanism of the lithium ion battery by intercalation and deintercalation of lithium ions can be utilized. The materials can be formed together to increase the operating voltage range of the hybrid capacitor.

In one example, 3d transition metal oxide (3d metal oxide) is used as a material formed on the electrode to utilize the operation mechanism of the lithium ion battery. The 3d transition metal oxide-based material may be represented as M'xM''yO4, and M'x and M''y are chromium (Chrome, Cr), manganese (Mn), cobalt (Cobalt, Co), Nickel (Ni) and copper (Copper, Cu) of the different materials.

In another example, a tin oxide-based material is used as a material that is formed with activated carbon on an electrode to utilize an operation mechanism of a lithium ion battery. As such tin oxide, materials such as tin oxide (SnO 2), stannerous pyrophosphate (Sn 2 P 2 O 7), SnPBO 6, SnPO 4 Cl, and the like may be used.

In another example, a tin based alloy is used as a material that is formed with activated carbon on an electrode to utilize an operation mechanism of a lithium ion battery. Such tin-based alloys include any one or more of a tin-iron (Iron, Fe) alloy, a tin-cobalt alloy, a tin-manganese alloy, a tin-vanadium (V) alloy, and a tin-titanium (Titianium, Ti) alloy. use.

In another example, Lithium Metal Nitride is used as a material that is formed with activated carbon on the electrode to utilize the operation mechanism of the lithium ion battery. Lithium molybdenum nitride (LiMoN 2) and lithium tungsten nitride (LiWN 2) may be used as the lithium metal nitride.

In another example, the carbon material is used as a material that is formed with activated carbon on the electrode to utilize the operation mechanism of the lithium ion battery. The carbon material may include any one or more of soft carbon, hard carbon, and carbon black.

In another example, a lithium-based metal is used as a material that is formed with activated carbon on an electrode to utilize an operation mechanism of a lithium ion battery. Such lithium-based materials may include any one or more of Li22Sb, Li22Sn5, Li22Pb5, Li22Pb series, Li22Si5, LiAl series, LiC series including LiC and LiC6, and Li.

Conventionally, only activated carbon having pores formed on its surface was used to increase the area of adsorption and desorption occurring at the electrode. As a result, a potential difference with the + electrode material is not large, resulting in a low operating voltage. In the case of using only lithium manganese oxide (LiMn2O2) as the positive electrode and activated carbon as the negative electrode, the voltage graph for the time shown in FIG. In the region, it can be seen that the voltage value charged as shown in the maximum is only 2.3V.

However, referring to FIG. 3, the potential difference ΔV obtained when the activated carbon and the material capable of utilizing the above-described operation mechanism of the lithium ion battery are formed together on the current collector plate of the negative electrode while the positive electrode material remains the same. Looking at it:-When 3d metal oxide is used as a material that can utilize the operation mechanism of lithium ions to the electrode, up to 3.3V, tin oxide as a material that can utilize the operating mechanism of lithium ions ) When using a series material, it is possible to use the operating mechanism of up to 3.5V, and when using a tin based alloy, up to 3.8V, which can utilize the operating mechanism of lithium ion. When using Lithium Metal Nitride, up to 3.9V, materials that can utilize the operation mechanism of Li-ion are Soft Carbon, Hard Carbon, And when using any one or more carbon materials of carbon black (Carbon Black) can be obtained up to 4.1V, up to 4.3V when using a lithium-based metal as a material that can utilize the operation mechanism of lithium ions.

Therefore, it is possible to solve the low operating voltage range, which is a problem of the prior art, and-has the advantage that the electric double layer capacitor by the activated carbon by forming a material that can utilize the operation mechanism of the lithium ion battery together with activated carbon in the electrode 100 Phosphoric fast operation speed and high instantaneous power and high energy density of lithium ion battery can be secured.

A method of forming the negative electrode of the hybrid capacitor according to the present invention will be described with reference to FIGS. 4 to 5. In one example, the active carbon layer 120 is formed on one surface of the current collector plate 110, and on the other side of the current collector plate, a material layer 130 may be formed to utilize the operation mechanism of the lithium ion battery. Form an electrode. In another example, as shown in FIG. 5, a mixed layer 125 in which a material capable of utilizing an operating mechanism of activated carbon and a lithium ion battery is formed on one surface and the other surface of the current collector plate 110 to form an electrode 100. Can be formed. In one example, forming a material layer that can utilize the operating mechanism of the activated carbon layer and the lithium ion battery in the current collector plate is performed by rolling. In another example, the formation of a material layer capable of utilizing the operating mechanism of the activated carbon layer and the lithium ion battery in the current collector plate is performed by spraying. In one example, the material layer and the activated carbon layer that can utilize the operation mechanism of the lithium ion battery formed on the current collector plate is formed to a thickness of 50 to 300μm. In one example, the current collector plate is formed of a metal thin film such as aluminum or copper.

While the embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, but can be manufactured in various forms, and the general knowledge in the art to which the present invention pertains. Those skilled in the art can understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, the above-described embodiments should be understood as illustrative in all respects, and the scope of the present invention should be determined based on the claims below.

10: hybrid capacitor
100: -electrode
110: current collector
120: activated carbon layer
125: material mixture layer that can utilize the operating mechanism of activated carbon and lithium ion battery
130: material layer that can utilize the operation mechanism of the lithium ion battery
200: + electrode

Claims (19)

Current collector; And
It includes a mixed layer formed on both sides of the current collector plate,
The mixed layer is provided with a mixture of activated carbon and a material that can utilize the operation mechanism of the lithium ion battery,
-Electrode for hybrid capacitors operating as a mixing mechanism of operation mechanism of lithium ion battery and operation mechanism of electric double layer capacitor. The method of claim 1,
A material capable of utilizing the operation mechanism of the lithium ion battery is a 3d metal oxide layer for hybrid capacitors-electrodes. The method of claim 2,
The formula of the 3d transition metal oxide is represented by M'xM''yO4, and M'x and M''y are chromium (Chrome, Cr), manganese (Mn), cobalt (Cobalt, Co), and nickel ( Nickel, Ni) and -electrode for a hybrid capacitor which is one of different materials selected from copper (Copper, Cu). The method of claim 1,
The material that can utilize the operation mechanism of the lithium ion battery is a -electrode for a hybrid capacitor which is a tin oxide-based material. 5. The method of claim 4,
The tin oxide-based material is a tin electrode (Tin Oxide, SnO 2), Stanus Pyrophosphate (Sannous Pyrophosphate, Sn 2 P 2 O 7), SnPBO 6, SnPO 4 Cl-electrode for a hybrid capacitor. The method of claim 1,
A material that can utilize the operation mechanism of the lithium ion battery is a tin-based alloy (tin-based alloy) -electrode for a hybrid capacitor. The method according to claim 6,
The tin-based alloy may be at least one of tin-iron (Iron, Fe) alloys, tin-cobalt alloys, tin-manganese alloys, tin-vanadium (Vandium, V) alloys, and tin-titanium (Titianium, Ti) alloys. Electrode for hybrid capacitor. The method of claim 1,
A material capable of utilizing the operation mechanism of the lithium ion battery is a lithium metal nitride (Lithium Metal Nitride) layer -electrode for a hybrid capacitor. 9. The method of claim 8,
The lithium metal nitride (Lithium Metal Nitride), at least one of lithium molybdenum nitride (LiMoN2), lithium tungsten nitride (LiWN2)-electrode for a hybrid capacitor. The method of claim 1,
The material that can utilize the operation mechanism of the lithium ion battery, for a hybrid capacitor, which is a carbon material containing at least one of soft carbon, hard carbon, and carbon black. electrode. The method of claim 1,
A material capable of utilizing the operation mechanism of the lithium ion battery is a lithium-based metal hybrid electrode for an electrode. The method of claim 11,
The lithium-based metal, Li22Sb, Li22Sn5, Li22Pb-based material including Li22Pb5, Li22Si5, LiAl-based material, LiC-based material including LiC and LiC6,-Electrode for a hybrid capacitor comprising at least one of Li. delete delete delete The method of claim 1,
The mixed layer of the material and the activated carbon that can utilize the operation mechanism of the lithium ion battery is rolled and formed on the current collector plate -electrode. + Electrode;
Electrolyte; And
Including a current collector plate and a mixed layer including a material capable of utilizing the operation mechanism of the lithium ion battery formed on the current collector plate and a form of a mixture of activated carbon,
It works by mixing mechanism of operation of lithium ion battery and operation of electric double layer capacitor
Hybrid capacitors. 18. The method of claim 17,
The + electrode,
Current collector; And
Hybrid capacitor comprising any one or more layers of lithium metal oxide and lithium metal phosphate formed on the current collector plate. 18. The method of claim 17,
Materials that can utilize the operation mechanism of the lithium ion battery formed on the current collector plate, 3d metal oxide (3d metal oxide), tin oxide (Tin Oxide) -based material, tin based alloy (Tin based alloy), lithium metal night A hybrid capacitor that is at least one of a carbon material including at least one of a lithium metal nitride, a soft carbon, a hard carbon, and a carbon black, and a lithium-based metal. .

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