KR100281828B1 - A hybrid type super rechargeable battery with lithium secondary batteries and super capacitors and its fabricating method - Google Patents

Abstract

The present invention is a hybrid super secondary battery manufacturing of a new concept incorporating a lithium secondary battery characteristics of high energy density but somewhat poor power density and cycle life characteristics and supercapacitor characteristics of low energy density but excellent output density and cycle life characteristics. The method relates to a hybrid super secondary battery according to the present invention has the advantages of high energy density, high power density and long cycle life. In addition, according to the present invention, the configuration of the hybrid type super secondary battery is changed to be suitable for the pulse power supply.

Description

HYBRID TYPE SUPER RECHARGEABLE BATTERY WITH LITHIUM SECONDARY BATTERIES AND SUPER CAPACITORS AND ITS FABRICATING METHOD}

The present invention relates to a novel super hybrid hybrid type secondary battery and a method for manufacturing the same, which are integrated by combining lithium secondary battery characteristics and supercapacitor characteristics.

The conventional lithium secondary battery has a high energy density (120 Wh / kg or more), but has a weak power density (about 200-250 W / kg) and cycle life characteristics (about 500 times). The room temperature type lithium secondary battery is first developed by Sony of Japan and is currently commercialized worldwide in lithium ion battery and lithium polymer battery which is expected to be commercialized within a few years.

Lithium-ion battery uses PE (polyethylene) or PP (polypropylene) separator as separator to impregnate organic solvent electrolyte to flow current, and roll and roll electrode and separator into cylindrical and square cylinders. (D. Linden, Handbook of Batteries, McGRAW-HILL INC., New York (1995)).

Lithium polymer battery uses solid polymer electrolyte which has two functions of membrane and electrolyte at the same time. It has the advantage of free design of battery shape, high energy density, and simple manufacturing process. However, ion of solid polymer electrolyte Since the conductivity is slightly lower than that of the organic solvent, high rate discharge characteristics and low temperature characteristics are disadvantageous. Recently, polyacrylonitrile (PAN) -based solid polymer electrolytes described in US Pat. Nos. 5,219,679 to KM Abraham et al. And US Pat. Nos. 5,240,790 to DL Chau et al. And polyols described in US Pat. Nos. 5,296,319 and 5,460,904 to AS Gozdz et al. Due to the development of vinylidene difluoride (PVdF) -based solid polymer electrolyte, the ion conductivity is 10 ^-3 S / cm or more at room temperature, and the lithium polymer battery has reached the commercialization stage, but the ion conductivity is 10 ^-2 S / cm or more. Since it is lower than the organic solvent electrolyte, there is a disadvantage that the high rate discharge characteristics and low temperature characteristics are poor compared to the lithium ion battery which is commercialized and widely used at present.

On the other hand, supercapacitors have recently been studied in S. Passerini and C.J. As described in the Proceedings of the Symposium on Electrochemical Capacitors, 95-29, 86, 187 (1996), published by Farahmandi et al., The power density is very high, over 1 KW / kg, and the cycle life is over 100,000 cycles. Is very low compared to a lithium ion battery at a maximum of about 5 Wh / kg has a lot of restrictions in the application field.

Recently J.R. As described in Miller, Proceedings of the Symposium on Electrochmical Capacitors, 95-29, 86, 246 (1996), high-rate discharge characteristics were investigated when the pulse discharge characteristics were studied by computer simulation method by connecting secondary batteries and capacitors in parallel. It can be seen that this is improved. Also J.G. As described in Keimel, U.S. Patent No. 5,591,212, and C. Pascual et al., U.S. Patent No. 5,710,504, a primary or secondary battery and a capacitor were connected to prevent the battery from being overloaded and improved high rate characteristics. Since the battery and the capacitor are manufactured independently of each other by attaching an electronic circuit, the battery and the capacitor may not be integrated, and both of them may cause inconvenience and increase in use. In particular, in recent years, even more problematic in the light and shortening trend of the battery, which is a very uncomfortable system that can not be used except in the application field where volume and weight are not important to the user.

The present invention relates to a method of manufacturing a hybrid super-secondary battery of a new concept integrated by combining the characteristics of the two batteries in order to take advantage of all the advantages of the lithium secondary battery and the supercapacitor as described above and to compensate for the disadvantages.

Figure 1a and 1b is a configuration diagram of a hybrid type super secondary battery according to the present invention, Figure 1a is a lithium secondary battery and a supercapacitor separately manufactured by stacking and separated into an insulating film 4-terminal hybrid super secondary manufactured 1B is a block diagram of a hybrid 2-second hybrid type super secondary battery manufactured by mixing an electrode for a lithium secondary battery active material and a supercapacitor active material to produce an electrode and stacking them.

2 is a graph showing the results of a high rate pulse discharge characteristic test for the hybrid type super secondary battery of the present invention and the battery of the comparative example.

Figure 3 is a graph showing the low temperature characteristics test results for the hybrid type super secondary battery of the present invention and the battery of the comparative example.

Figure 4 is a graph showing the electrode capacity and life test results for the hybrid type super secondary battery of the present invention and the battery of the comparative example.

According to the present invention, a lithium ion battery or a lithium polymer battery is manufactured by stacking in order of an anode / separation membrane or a solid polymer electrolyte / cathode / separation membrane or a solid polymer electrolyte / anode, and an insulating polymer film is formed thereon to completely insulate electrical insulation. Next, a supercapacitor stacked in the order of anode / separator / cathode / separator / anode is manufactured, and a lithium secondary battery and a supercapacitor are inserted into a battery case at once to provide an integrated 4-terminal battery and a method of manufacturing the same. .

In addition, according to the present invention, an integrated electrode is manufactured by mixing an active material for a lithium secondary battery and an active material for a supercapacitor as an active material, and stacked in the order of a cathode / separation membrane or a solid polymer electrolyte / cathode / separation membrane or a solid polymer electrolyte / anode. A two-terminal battery and a method of manufacturing the same are provided.

The present invention relates to a hybrid type super secondary battery integrated with the characteristics of a lithium secondary battery and a supercapacitor and a method of manufacturing the same.

Lithium secondary battery of the present invention is composed of a lithium ion battery or a lithium polymer battery of the laminated form, the lithium ion battery is laminated a plurality of layers in the order of the anode / separator / cathode / separator / anode for lithium ion battery and then welding the terminals It is prepared by injecting an organic solvent electrolyte for a lithium secondary battery. Lithium polymer batteries are manufactured by stacking several layers in the order of positive electrode / solid polymer electrolyte / cathode / solid polymer electrolyte / anode for lithium polymer battery, welding terminals, and without injecting or injecting organic solvent electrolyte for lithium secondary battery.

LiCoO ₂ , LiMn ₂ O ₄ , LiNiO ₂ , V ₆ O _13, V ₂ O _5, etc. may be used as the positive electrode active material. As the negative electrode active material, graphite, coke, hard carbon, tin oxide and those lithiated thereof, Lithium metal, lithium alloy, etc. can be used. As the separator, a porous polymer membrane such as PE (polyethylene), PP (polypropylene) or PE / PP bilayer can be used, and the solid polymer electrolyte is polyethylene oxide (PEO), polyethylene glycol (PEG), and polyacrylonitrile (PAN). ), Polyvinylidene difluoride (PVdF) system, or a polymer blend thereof, an EC (ethylene carbonate)-DMC (dimethyl carbonate) solution in which lithium salt is dissolved, EC (ethylene carbonate) in which lithium salt is dissolved )-EMC (enthyl methyl carbonate) solution or lithium salt dissolved EC (ethylene carbonate)-DEC (diethyl carbonate) solution, MA (methyl acetate), MP (methyl propionate), EA (enthyl acetate) or EP (ethyl propionate) may be used which consists of a solution with or without addition of propionate). Here, the lithium salt is preferably LiPF ₆ , LiClO ₄ , LiCF ₃ SO ₃ or LiBF ₄ . The organic solvent electrolyte is EC (ethylene carbonate)-DMC (dimethyl carbonate) solution in which lithium salt is commonly used in lithium secondary battery, EC (ethylene carbonate)-EMC (enthyl methyl carbonate) solution or lithium salt in which lithium salt is dissolved To this dissolved EC (ethylene carbonate)-DEC (diethyl carbonate) solution, MA (methyl acetate), MP (methyl propionate), EA (enthyl acetate) or EP (ethyl propionate) is added or not added. It may be used, wherein the lithium salt is preferably LiPF ₆ , LiClO ₄ , LiCF ₃ SO ₃ or LiBF ₄ . For example, a solution of ethylene carbonate (EC)-dimethyl carbonate (DMC), ethylene carbonate (EC)-diethyl carbonate (DEC), ethylene carbonate (EC)-ethyl methyl carbonate (EMC) in which 1M LiPF ₆ is dissolved use.

The lithium secondary battery and the supercapacitor are separated into a polymer film such as a PET film having no pores and insulation so that there is no short circuit and no leakage current flows.

The supercapacitor is made on the polymer membrane, and the supercapacitor is manufactured by stacking several layers in the order of the anode / separation membrane / cathode / anode for the supercapacitor, welding the terminals, and injecting an organic solvent electrolyte or an aqueous alkali solution for the supercapacitor. The active material of the positive electrode and the negative electrode is the same, and the material to be used is a carbon material such as activated carbon or carbon fiber having a very large surface area, and nano-sized particles such as RuO ₂ , MoO ₂ or V ₂ O ₅ coated on these materials. Use one. In addition, conductive polymers such as polyaniline (PAn-polyaniline) and polypyrrole (PPy-polypyrrole) may be used. As the separator, a separator such as PE or PP used in a lithium ion battery or a solid polymer electrolyte for a lithium polymer battery may be used. The organic solvent electrolyte is propylene carbonate (PC) in which lithium salts such as lithium triplate (LiCF ₃ SO ₃ ) or lithium perchlorate (LiCiO ₄ ) are dissolved, propylene carbonate in which tetraethylammonium tetrafluoroborate (TEABF ₄ ) is dissolved, or Sulfolan / Acetonitrile solution in which tetraethylammonium methylsulfonate (TEAMS) is dissolved is used, and as aqueous alkali solution, KOH, LiOH, NaOH, H ₂ SO ₄ , HCl or NaCl solution is used. do.

Supercapacitors have a low energy density but very high output density, so when they are connected in parallel with lithium secondary batteries, the amount of electricity stored in the supercapacitor is released when a high output is required, and they are stored in the lithium secondary battery when a low output is required. The supercapacitor is charged. Supercapacitors can be used for digital pulse power supply because they can be charged and discharged quickly. The terminals of the battery consist of four terminals: two positive and negative terminals of the lithium secondary battery, two positive and negative terminals of the supercapacitor, and the terminals of the same polarity are connected in parallel according to the current pattern of the equipment used. There is a method of using and connecting a terminal with an electronic control circuit.

In addition, according to the present invention, an integrated electrode is prepared by mixing an active material for a lithium secondary battery and an active material for a supercapacitor as an active material, and stacked in the order of a cathode / separation membrane or a solid polymer electrolyte / cathode / separation membrane or a solid polymer electrolyte / anode. One terminal integrated battery can be manufactured.

The most important thing in constructing a hybrid super secondary battery by manufacturing an integrated electrode using a mixture of an active material for a lithium secondary battery and an active material for a supercapacitor as an active material is the selection of the active material. Higher is a conductive polymer. The conductive polymer is a material showing the characteristics of the capacitor and the lithium secondary battery. When the battery is composed of these materials, the characteristics of the supercapacitor and the lithium secondary battery appear. However, the battery of the commercialization level has not yet appeared only by the conductive polymer itself. Therefore, since the present invention is difficult to commercialize only the conductive polymer itself, the cathode active material for a lithium secondary battery, polyaniline (PAn), polypyrrole (PPy), polyacetylene (PA), polythiophene (PTh), polyparaphenylene (PPP) The positive electrode is prepared by mixing a conductive polymer such as) as a positive electrode active material or a mixture of a conductive polymer and an active material such as activated carbon and carbon fiber for a supercapacitor as a positive electrode active material, and a negative electrode as a negative electrode active material for a lithium secondary battery. To prepare a battery by separating a positive electrode and a negative electrode with a lithium ion battery separator or a solid polymer electrolyte for a lithium polymer battery, and injecting an organic solvent electrolyte to form a hybrid battery having two characteristics of a supercapacitor and a lithium secondary battery. A super secondary battery can be manufactured.

Hereinafter, the present invention will be described in detail with reference to the following Examples, which are only illustrative of the present invention, but the present invention is not limited thereto.

Example 1

The lithium ion battery was manufactured according to a conventional method. Specifically, the carbon anode is Gr. (Graphite) 6g, AB (acetylene black) 0.3g, PVdF 0.4g composition is mixed with 4g NMP (N-methyl-2-pyrrolidinone) and 4g acetone, when the viscosity of honey is obtained doctor on a copper sheet Cast by the blade method and dried at room temperature and 80 ℃ for 12 hours, and then rolled at a pressure of 1 kg / cm ² to obtain an electrode. LiCoO ₂ anode was mixed with 4g NMP and 4g acetone with 5.7g of LiCoO ₂ , 0.6g of AB and 0.4g of PVdF, and then cast on a thin sheet of aluminum by a doctor blade method when the viscosity was obtained as honey. After drying for 12 hours at 1 kg / cm ² to obtain a electrode by rolling. The lithium ion battery was prepared by incorporating a carbon cathode, a PP separator, and a LiCoO ₂ anode and injecting an EC-EMC solution in which 1M LiPF ₆ was dissolved. After the lithium ion battery was prepared, complete solution blocking and electrical insulation were performed with a PET film, and then an organic electrolyte supercapacitor was prepared thereon. Looking at the manufacturing method of the organic electrolyte supercapacitor in detail, 10% PTFE (polytetrafluoroethylene) as a binder was added to Ketjen Black-600JD (manufactured by Kurea Co., Ltd.) as an active material, and ethanol, a solvent, was added and mixed for about 3 hours. After mixing, the solvent was evaporated under vacuum for 24 hours, and the dried electrode material was placed on an aluminum mesh and rolled at a pressure of 1 kg / cm ² to prepare an activated carbon electrode. This electrode was used as a positive electrode and a negative electrode, and a PP separator was inserted therebetween, and a supercapacitor was prepared by injecting a PC solution in which 1M LiClO ₄ was dissolved. The lithium ion battery and the supercapacitor were put in the same package and vacuum sealed to prepare a hybrid super secondary battery. At this time, the electrode terminal comes out of two terminals in a lithium ion battery, and two terminals of a negative electrode and a positive electrode in a supercapacitor, respectively, and four terminals come out. The charge / discharge test of the battery was carried out by a charge / discharge method of charging with a C / 2 constant current, 4.2 V constant voltage and discharging at a 1C discharge rate to investigate electrode capacity and cycle life based on the positive electrode.

Example 2

The lithium polymer battery was manufactured according to a conventional method. Specifically, the carbon cathode is Gr. (Graphite) 6g, AB (acetylene black) 0.3g, PAN gel solid polymer electrolyte 3.7g, EC-DMC solution 10g of the composition was mixed with a doctor blade method on the copper foil when the same viscosity as honey obtained After drying at room temperature for 24 hours, the resultant was rolled at a pressure of 1 kg / cm ² to obtain an electrode. The LiCoO ₂ anode was mixed with a composition of 5.7 g of LiCoO ₂ , 0.6 g of AB, 3.7 g of PAN gel solid polymer electrolyte, and 10 g of EC-DMC solution, and then cast on a thin sheet of aluminum by a doctor blade method when a viscosity was obtained. After drying at room temperature for 24 hours, the resultant was rolled at a pressure of 1 kg / cm ² to obtain an electrode. The lithium polymer battery was prepared by configuring a carbon anode, a PAN gel solid polymer electrolyte, and a LiCoO ₂ cathode. After the lithium polymer battery was prepared, complete solution blocking and electrical insulation were performed using a PET film, and then an organic electrolyte supercapacitor was prepared thereon. Looking at the manufacturing method of the organic electrolyte supercapacitor in detail, 10% of PTFE (polytetrafluoroethylene) binder was added to Ketjen Black-600JD (manufactured by Kurea, Japan) as an active material, and ethanol, a solvent, was added and mixed for about 3 hours. After mixing for 24 hours, the solvent was evaporated under vacuum to mix, and the dried electrode material was placed on an aluminum mesh and rolled at a pressure of 1 kg / cm ² to prepare an activated carbon electrode. The electrode was used as a positive electrode and a negative electrode, and a PAN gel-type solid polymer electrolyte was placed therebetween, and a supercapacitor was prepared by injecting a PC solution in which 1M LiClO ₄ was dissolved. The lithium polymer battery and the supercapacitor were put in the same package and vacuum sealed to prepare a hybrid type super secondary battery. At this time, the electrode terminal comes out of two terminals of the lithium polymer battery, and two terminals of the negative and positive electrodes of the supercapacitor, and the four terminals come out. The charge / discharge test of the battery was carried out by the charge / discharge method of charging with a C / 2 constant current, 4.2 V constant voltage and discharging at a 1C discharge rate to investigate electrode capacity and cycle life based on the positive electrode.

Example 3

The lithium polymer battery was manufactured according to a conventional method. Specifically, the carbon cathode was mixed with 6 g of Gr. (Graphite), 0.3 g of AB (acetylene black), 3.7 g of PAN gel solid polymer electrolyte, and 10 g of EC-DMC solution. When the same viscosity as honey was obtained, it was cast on a copper foil by a doctor blade method, dried at room temperature for 24 hours, and then rolled at a pressure of 1 kg / cm ² to obtain an electrode. LiCoO ₂ anode was mixed with LiCoO ₂ 5.7g, AB 0.6g, PAN gel solid polymer electrolyte, 3.7g, EC-DMC solution 10g, and then cast on the aluminum sheet by the doctor blade method when the viscosity was obtained as honey. After drying at room temperature for 24 hours, the resultant was rolled at a pressure of 1 kg / cm ² to obtain an electrode. The lithium polymer battery was prepared by forming a carbon anode, a PAN gel solid polymer electrolyte, and a LiCoO ₂ cathode. After the lithium polymer battery was prepared, complete solution blocking and electrical insulation were performed using a PET film, and then an aqueous supercapacitor was prepared thereon. Looking at the manufacturing method of an aqueous supercapacitor in detail, 10% PTFE (polytetrafluoroethylene) as a binder was added to Ketjen Black-600JD (manufactured by Kurea, Japan) as an active material, and ethanol as a solvent was added and mixed for about 3 hours. After mixing for 24 hours, the solvent was evaporated under vacuum to mix, and the dried electrode material was placed on an aluminum mesh and rolled at a pressure of 1 kg / cm ² to prepare an activated carbon electrode. The electrode was used as a positive electrode and a negative electrode, and an aqueous solution was placed in a PP separator, and a 6 M KOH solution was injected thereinto to prepare a single cell, and the single cell was separated by a PET insulating film to connect four single cells in series to prepare a supercapacitor. . The lithium polymer battery and the supercapacitor were put in the same package and vacuum sealed to prepare a hybrid type super secondary battery. At this time, the electrode terminal comes out of two terminals of the lithium polymer battery, and two terminals of the negative and positive electrodes of the supercapacitor, and the four terminals come out. The charge / discharge test of the battery was carried out by the charge / discharge method of charging with a C / 2 constant current and 4.2V constant voltage and discharging at a 1C discharge rate to investigate electrode capacity and cycle life based on the positive electrode.

Example 4

As a cathode active material of a lithium ion battery, LiCoO ₂ and a conductive polymer were mixed to prepare a hybrid super secondary battery in the form of a lithium ion battery. The carbon cathode is Gr. (Graphite) 6g, AB (acetylene black) 0.3g, PVdF 0.4g composition is mixed with 4g NMP (N-methyl-2-pyrrolidinone) and 4g acetone and when the viscosity of honey is obtained doctor on a copper sheet Cast by the blade method and dried at room temperature and 80 ℃ for 12 hours, and then rolled at a pressure of 1 kg / cm ² to obtain an electrode. The anode was mixed with a composition of 4.6 g of LiCoO ₂ , 1.2 g of polypyrrole conductive polymer (PPy), 0.5 g of AB, and 0.4 g of PVdF in 4 g NMP and 4 g acetone, and then the doctor blade method on the aluminum sheet when the viscosity was obtained as honey. After casting to dry at room temperature and 80 ℃ for 12 hours, a pressure of 1 kg / cm ² was rolled to obtain an electrode. The hybrid super _secondary battery was prepared by incorporating a carbon cathode, a PP separator, a LiCoO ₂ + PPy anode, and injecting an EC-EMC solution in which 1M LiPF ₆ was dissolved. The charge / discharge test of the battery was carried out by a charge / discharge method of charging at a C / 2 constant current, 4.2V constant voltage and discharging at a 1C discharge rate to investigate electrode capacity and cycle life based on the positive electrode.

Example 5

As a cathode active material of a lithium polymer battery, LiCoO ₂ and a conductive polymer were mixed to prepare a hybrid super secondary battery in the form of a lithium polymer battery. The carbon cathode is Gr. (graphite) 6g, AB (acetylene black) 0.3g, PAN gel solid polymer electrolyte 3.7g, EC-DMC solution 10g of the composition was mixed with a doctor blade method on the copper foil when the same viscosity as honey obtained After drying at room temperature for 24 hours, the resultant was rolled at a pressure of 1 kg / cm ² to obtain an electrode. The anode was mixed with 4.6 g of LiCoO ₂ , 1.2 g of polypyrrole conductive polymer (PPy), 0.5 g of AB, 3.7 g of PAN gel solid polymer electrolyte, and 10 g of EC-DMC solution. Casting on a thin plate by a doctor blade method, dried at room temperature for 24 hours and then rolled at a pressure of 1 kg / cm ² to obtain an electrode. The hybrid super _secondary battery was manufactured by configuring a carbon cathode, a PAN gel solid polymer electrolyte, and a LiCoO ₂ + PPy anode. The charge / discharge test of the battery was carried out by the charge / discharge method of charging with a C / 2 constant current, 4.2 V constant voltage and discharging at a 1C discharge rate to investigate electrode capacity and cycle life based on the positive electrode.

Example 6

A lithium super polymer battery of a lithium polymer battery was manufactured by using Li metal as a negative electrode of a lithium polymer battery and a positive electrode active material mixed with LiCoO ₂ and a conductive polymer. The anode was mixed with 4.6 g of LiCoO ₂ , 1.2 g of polypyrrole conductive polymer (PPy), 0.5 g of AB, 3.7 g of PAN gel solid polymer electrolyte, and 10 g of EC-DMC solution. Casting on a thin plate by a doctor blade method, dried at room temperature for 24 hours and then rolled at a pressure of 1 kg / cm ² to obtain an electrode. The hybrid super _secondary battery was manufactured by configuring a Li cathode, a PAN gel solid polymer electrolyte, and a LiCoO ₂ + PPy anode. The charge / discharge test of the battery was carried out by the charge / discharge method of charging at a C / 2 constant current and 4.2 constant voltage and discharging at a 1C discharge rate.

Comparative Example 1

Lithium-ion battery (LIB) was manufactured according to a conventional method. Specifically, the carbon cathode was composed of 6 g of Gr (graphite), 0.3 g of AB (acerylene black), and 0.4 g of PVdF, and 4 g of NMP (N-emthyl-2-). After mixing with pyrrolidinone) and 4 g acetone, when the same viscosity as honey was obtained, casting was carried out by a doctor blade method on a copper foil, dried at room temperature and 80 ° C for 12 hours, and then rolled at a pressure of 1 kg / cm ² . Got it. After mixing LiCoO ₂ , 5.7g, AB 0.6g, and PVdF 0.4g in 4g NMP and 4g acetone, when the viscosity was obtained as honey, it was cast on rolled aluminum blade on the aluminum sheet by the doctor blade method. It was prepared by injecting dissolved EC-EMC solution by rolling at a pressure of 1 kg / cm ² after drying for a time. The charge / discharge test of the battery was prepared by charging with a C / 2 constant current, 4.2 V constant voltage and discharging at a 1 C discharge rate. The charge / discharge test of the battery was carried out by charging with a C / 2 constant current, 4.2 V constant voltage and charging and discharging at 1C discharge rate to investigate the electrode capacity and cycle life based on the positive electrode.

Comparative Example 2

The lithium polymer battery was manufactured according to a conventional method. Specifically, the carbon cathode is Gr. (graphite) 6g, AB (acetylene black) 0.3, PAN-based solid polymer electrolyte 3.7g, EC-EMC solution 10g of the composition was mixed, when the viscosity of the honey is obtained by casting on a copper foil by a doctor blade method at room temperature After drying for 24 hours at 1 kg / cm ² to obtain a electrode by rolling. The LiCoO ₂ anode was mixed with a composition of 5.7 g of LiCoO ₂ , 3.7 g of AB 0.6g PAN gel solid polymer electrolyte, and 10 g of EC-DMC solution, and then cast on a thin sheet of aluminum by a doctor blade method when the viscosity was obtained. After drying at room temperature for 24 hours, the resultant was rolled at a pressure of 1 kg / cm ² to obtain an electrode. The lithium polymer battery was prepared by configuring a carbon anode, a PAN gel solid polymer electrolyte, and a LiCoO ₂ cathode. The charge / discharge test of the battery was carried out by the charge / discharge method of charging with a C / 2 constant current and 4.2 V constant voltage and discharging at a 1 C discharge rate. The electrode capacity and cycle life based on the positive electrode were investigated.

Example 7

The high rate pulse discharge characteristics of the hybrid type secondary batteries manufactured according to Examples 1, 2, 4 and 5 and the lithium secondary batteries prepared according to Comparative Examples 1 and 2 were charged with C / 2 constant current and 4,2 V constant voltage. , 10C 10 ms, 0C 90 ms (average 1C discharge rate) by the charge and discharge method to measure the voltage at 10C discharge is shown in Fig. From the graph of Figure 2, the high rate pulse discharge characteristics (44 minutes up to 3.0V) of the hybrid type super secondary battery manufactured according to the embodiment of the present invention is a high rate pulse discharge characteristics (3.0V) of the lithium secondary battery prepared according to the comparative example 12 minutes) is very excellent.

Example 8

The low-temperature characteristics at -10 ° C of the hybrid-type super secondary batteries prepared according to Examples 2 and 6 and the lithium polymer batteries prepared according to Comparative Example 2 were charged with C / 2 constant current, 4.2 V constant voltage, and C / 5 constant current. It measured by the charging / discharging method of discharging at and shown in FIG. From the graph of Figure 3, it can be seen that the low-temperature characteristics of the hybrid type super secondary battery manufactured according to the embodiment of the present invention is very excellent compared to the low temperature characteristics of the lithium polymer battery prepared according to the comparative example.

Example 9

The charge / discharge characteristics of the hybrid type super secondary batteries prepared according to Examples 1 to 6 and the lithium polymer batteries prepared according to Comparative Examples 1 and 2 were charged with C / 2 constant current and 4.2V constant voltage and discharged with 1C constant current. It measured by the discharge method and shown in FIG. From the graph of Figure 4, it can be seen that the charge and discharge characteristics of the hybrid type super secondary battery prepared according to the embodiment of the present invention is superior to the charge and discharge characteristics of the lithium polymer battery prepared according to the comparative example.

As shown in Examples 7 to 9, the hybrid type super secondary battery according to the present invention utilizes the advantages of a lithium secondary battery and a supercapacitor, and exhibits high rate pulse discharge characteristics, low temperature characteristics, and cycle life characteristics. It is also very suitable for electric vehicle power.

Claims (24)

A lithium ion battery or a lithium polymer battery stacked in the order of an anode / separator or a solid polymer electrolyte / cathode / a separator / solid polymer electrolyte / anode; An insulating polymer film having no pores formed on the battery; And a supercapacitor stacked in the order of the anode / separation membrane / cathode / separation membrane / anode formed on the polymer membrane, and integrated into one battery case. According to claim 1, wherein the positive electrode active material is a hybrid type super secondary battery, characterized in that any one selected from the group consisting of LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , V ₂ O ₅ and V ₆ O ₁₃ . The hybrid super-secondary battery according to claim 1, wherein the negative electrode active material is any one selected from the group consisting of graphite, coke, hard carbon, tin oxide, lithium compounds thereof, lithium metal and lithium alloy. The hybrid type secondary battery of claim 1, wherein the separator is any one selected from the group consisting of PE (polyethylene), PP (polypropylene), and PE / PP bilayer. The method of claim 1, wherein the solid polymer electrolyte is polyethylene oxide (PEO), polyethylene glycol (PEG), polyacrylonitrile (PAN), polyvinylidene difluoride (PVdF) or polymer blends thereof EC (ethylene carbonate)-DMC (dimethyl carbonate) solution, lithium salt dissolved EC (ethylene carbonate)-EMC (ethyl methyl carbonate) solution or lithium salt dissolved EC (ethylene) carbonate)-a hybrid super characterized in that it consists of a solution with or without addition of MA (methyl acetate), MP (methyl propionate), EA (ethyl acetate) or EP (ethyl propionate) to a DEC (diethyl carbonate) solution Secondary battery. The battery according to any one of claims 1 to 4, wherein the battery is a lithium ion battery prepared by injecting an organic solvent electrolyte for a lithium secondary battery after stacking several layers in the order of anode / separation membrane / cathode / separation membrane / anode. Hybrid type super secondary battery, characterized in that. The method of claim 6, wherein the organic solvent electrolyte is EC (ethylene carbonate)-DMC (dimethyl carbonate) solution in which lithium salt is dissolved, EC (ethylene carbonate)-EMC (ethyl methyl carbonate) solution or lithium salt in which lithium salt is dissolved The dissolved EC (ethylene carbonate) -DEC (diethyl carbonate) solution is a solution in which MA (methyl acetate), MP (methyl propionate), EA (ethyl acetate) or EP (ethyl propionate) is added or not added. Hybrid type super secondary battery. The method of claim 1, 2, 3, or 5, wherein the battery is laminated with a plurality of layers in the order of positive electrode / solid polymer electrolyte / negative electrode / solid polymer electrolyte / anode, and then the organic solvent electrolyte for a lithium secondary battery Hybrid type super secondary battery, characterized in that the lithium polymer battery prepared with or without a slight injection. The method of claim 8, wherein the organic solvent electrolyte is EC (ethylene carbonate)-DMC (dimethyl carbonate) solution in which lithium salt is dissolved, EC (ethylene carbonate)-EMC (ethyl methyl carbonate) solution or lithium salt in which lithium salt is dissolved The dissolved EC (ethylene carbonate) -DEC (diethyl carbonate) solution is a solution in which MA (methyl acetate), MP (methyl propionate), EA (ethyl acetate) or EP (ethyl propionate) is added or not added. Hybrid type super secondary battery. The hybrid type super secondary battery according to claim 5, 7 or 9, wherein the lithium salt is LiPF ₆ , LiClO ₄ , LiCF ₃ SO _3, or LiBF ₄ . The method of claim 1, wherein the positive electrode and the negative electrode active material of the supercapacitor is any one selected from the group consisting of RuO ₂ , MoO ₂ and V ₆ O ₅ on any one selected from the group consisting of activated carbon, carbon fiber and carbon material. Hybrid type super-secondary battery, characterized in that the nanoparticles of the coating material or conductive polymer. The hybrid super-secondary battery of claim 1, wherein the separator of the supercapacitor is a separator for a lithium ion battery or a solid polymer electrolyte for a lithium polymer battery. The method of claim 1, 11 or 12, wherein the supercapacitor is prepared by stacking several layers in the order of anode / separator / cathode / separator / anode and then injecting an organic solvent electrolyte or alkaline aqueous solution for the supercapacitor. Hybrid type super secondary battery, characterized in that. The method of claim 13, wherein the organic solvent electrolyte for the supercapacitor is Sulfolan / dissolved PC (propylene carbonate), TEABF ₄ (tetraethylammonium tetrafluoroborate) dissolved in PC (propylene carbonate) or TEAMS (tetraethylammoninum methylsulfonate) dissolved Hybrid super secondary battery, characterized in that the Acetonitrile solution. The hybrid super secondary battery of claim 13, wherein the alkaline aqueous solution is a KOH, LiOH, NaOH, H ₂ SO ₄ , HCl, or NaCl solution. In the order of the positive electrode / separator or a mixture of the positive active material for a lithium secondary battery and the active material for a supercapacitor or the negative electrode active material / separator for a solid polymer electrolyte / lithium secondary battery or a positive electrode mixed with a positive active material for a solid polymer electrolyte / lithium secondary battery and an active material for a supercapacitor. Hybrid type super-secondary battery, characterized in that the integrated and laminated by vacuum-sealing after putting the organic solvent electrolyte. 17. The method of claim 16, wherein the positive electrode in which the positive electrode active material for a lithium secondary battery and the active material for a supercapacitor is mixed with a conductive polymer such as polyaniline, polypyrrole, polyacetylene, polythiophene, and polyparaphenylene in a positive electrode active material for a lithium secondary battery. A hybrid type super secondary battery comprising a positive electrode or a positive electrode mixed with a conductive polymer, an active carbon for a supercapacitor, and a carbon fiber. 17. The hybrid type secondary battery of claim 16, wherein the separator is any one selected from the group consisting of PE (polyethylene), PP (polypropylene), and PE / PP bilayer. The method of claim 16, wherein the solid polymer electrolyte, polyethylene oxide (PEO), polyethylene glycol (PEG), polyacrylonitrile (PAN), polyvinylidene difluoride (PVdF) or polymer blends thereof EC (ethylene carbonate)-DMC (dimethyl carbonate) solution, lithium salt dissolved EC (ethylene carbonate)-EMC (ethyl methyl carbonate) solution or lithium salt dissolved EC (ethylene) carbonate)-a hybrid super characterized in that it consists of a solution with or without addition of MA (methyl acetate), MP (methyl propionate), EA (ethyl acetate) or EP (ethyl propionate) to a DEC (diethyl carbonate) solution Secondary battery. The method of claim 16, wherein the organic solvent electrolyte is EC (ethylene carbonate)-DMC (dimethyl carbonate) solution in which lithium salt is dissolved, EC (ethylene carbonate)-EMC (ethyl methyl carbonate) solution or lithium salt in which lithium salt is dissolved The dissolved EC (ethylene carbonate) -DEC (diethyl carbonate) solution is a solution in which MA (methyl acetate), MP (methyl propionate), EA (ethyl acetate) or EP (ethyl propionate) is added or not added. Hybrid type super secondary battery. The hybrid super secondary battery of claim 20, wherein the lithium salt is LiPF ₆ , LiClO ₄ , LiCF ₃ SO _3, or LiBF ₄ . Forming a lithium ion battery or a lithium polymer battery by laminating in order of an anode / separator or a solid polymer electrolyte / cathode / a separator or a solid polymer electrolyte / anode; Forming an insulating polymer film without pores on the battery; And a supercapacitor stacked in the order of the anode / separation membrane / cathode / separation membrane / anode formed on the polymer membrane into one battery case to integrate the supercapacitor. In the order of the positive electrode / separator or a mixture of the positive active material for a lithium secondary battery and the active material for a supercapacitor or the negative electrode active material / separator for a solid polymer electrolyte / lithium secondary battery or a positive electrode mixed with a positive active material for a solid polymer electrolyte / lithium secondary battery and an active material for a supercapacitor. Method of manufacturing a hybrid type super-secondary battery, characterized in that the laminated and then the organic solvent electrolyte is sealed by vacuum sealing to integrate. A method of using a hybrid type super secondary battery according to any one of claims 1 to 21 as a power source or by attaching an electronic control circuit.