KR101624861B1 - Flash module for mobile device using flexible thin-film type super-capacitor and mobile device having the super-capacitor - Google Patents

Abstract

The present invention provides a flash module for mobile terminal using a super-capacitor and a mobile terminal having the super-capacitor. In a flash module for mobile terminal using a thin-film type super-capacitor which charges power for a flash operation by power supply and performs a flash operation by a luminescence request, the flash module includes an LED device which emit light by a flash current; a flexible thin-film supper-capacitor device which is charged according to the activation of the power supply and supplies the flash current according to a control signal; and a control part which activates the power supply to the supper-capacitor device and generates the control signal according to the luminescence request. So, superior performance can be maintained.

Description

TECHNICAL FIELD [0001] The present invention relates to a flash module for a mobile terminal using a flexible thin film type super capacitor, and a mobile terminal having the flash module. [0002]

The present invention relates to a flash module for a mobile terminal using a flexible thin film type supercapacitor and a mobile terminal having the flexible module. More particularly, the present invention relates to a flash module for forming a current collector having excellent adhesion on a flexible base film, The present invention relates to a flash module for a mobile terminal using a flexible thin film type super capacitor capable of maintaining excellent performance while having flexibility, and a mobile terminal having the flash module.

The digital camera provided in the portable terminal needs to secure a sufficient amount of light at the time of photographing so that the subject can be photographed vividly. Conventionally, a conventional Xenon flash is used in order to secure a light quantity, but since a xenon flash is difficult to manufacture in a small size, an LED element is used as a light emitting element of a flash module in a portable terminal. Meanwhile, according to the improvement of the performance of the LED device, it is difficult to meet the power demand of the LED device as the power source for the conventional portable terminal, and therefore, a method of using the super capacitor as the power source of the LED device capable of instantaneously providing high power Research.

Generally, like the electrodes of the capacitor, the electrodes such as the secondary battery and the electrochemical capacitor are largely composed of an active material for generating an electrochemical reaction and a current collector for transferring electrons generated from the active material to an external circuit. It is preferable that the current collector has a high electrical conductivity with a minimum resistance so that the flow of electrons supplied from the active material is not disturbed. In addition, since the electrons move through the interface between the active material and the active material, it is required to have a wide contact area as much as possible, and the contacted active material is not easily peeled off. Thus, mechanical and electrical characteristics are maintained even under repeated charging and discharging conditions for a long time It is desirable to have a long lifetime.

Electrodes of currently used secondary batteries and electrochemical capacitors are generally formed by applying a slurry containing an active material, a conductive material, a binder, or a binder to an aluminum foil current-etched electrochemically, Lt; / RTI >

In addition, in recent years, electronic devices that are folded or worn have appeared, and in particular, there is a growing need for a flexible capacitor device.

Prior art related to this technique is disclosed in Japanese Patent Application Laid-Open No. 2000-357631 (2000.12.26), Japanese Patent Application Laid-Open No. 2010-098109 (2010.04.30).

However, in this method, cavities may be formed because the inside of pits formed by etching are not completely filled, and electrode resistance is increased due to the bonding agent used. As time elapses, And there is a concern that the flexibility is lacking.

As described above, the present invention is directed to a flash module for a mobile terminal using a flexible thin film type super capacitor which is very thin and flexible while maintaining high electrical conductivity and high adhesion, And to provide a mobile terminal.

According to a first aspect of the present invention, there is provided a flash module for a mobile terminal using a supercapacitor that charges power for a flash operation through power supply and performs a flash operation by a flash request An LED element emitting light by a flash current; A flexible thin film type supercapacitor element charged according to the activation of the power supply and supplying the flash current according to a control signal; And a control unit for activating the power supply to the supercapacitor device and generating the control signal in response to the light emission request. The present invention also provides a flash module for a mobile terminal using the supercapacitor.

At this time, the supercapacitor element includes two flexible base films; A separation membrane interposed between the base films; And an active material layer formed on each of the base films.

The current collector may further include a current collector formed between the base film and the active material layer, and the current collector may be formed of a metal layer formed after the surface of the base film is processed.

At this time, the active material layer may be formed of a material formed by coating a graphene oxide solution on the current collector, and then heating and applying heat and heat treatment, or a material selected from a carbon material, a carbon hybrid material, a metal oxide, a nitride, a sulfide, and a conductive polymer . ≪ / RTI >

At this time, the base film may be formed of a polyphenylene sulfide (PPS) film, a polypropylene (PP) film, a polyethylenetaphthalate (PET) film, a polycarbonate (PC) film, a polyethylene naphthalate (PEN) film, and a polyethylene terephthalate PET) film.

At this time, the base film may be a film on which a metal containing aluminum is deposited.

At this time, the base film may be surface-treated.

The metal layer may include at least one selected from the group consisting of Ni, Pt, Ag, Au, Cu, Al, Pd, and Ir. can do.

The electrolyte may be an aqueous electrolyte or a non-aqueous (organic, ionic liquid) electrolyte, and the electrolyte may be in the form of liquid, gel or solid.

The collector may further include a current collector formed between the base film and the active material layer. The collector may be formed of a metal or a carbon material by one or more of a plating method, a vacuum deposition method, a screen printing method and a stamping method. And a method of depositing a conductor comprising the same.

At this time, the two base films are provided with a thermal adhesive film so as to surround the active material formed in the middle, the thermal adhesive films formed on the two base films are bonded to each other, the thermal adhesive film includes an adhesive, The adhesive may comprise at least one selected from the group consisting of acrylate, silicone, epoxy and thermal adhesive.

At this time, the separation membrane may be one selected from the group consisting of polyethylene (PE), polypropylene (PP), nonwoven fabric, and electrolyte integral separator.

Further, the supercapacitor element includes two flexible base films; A separation membrane interposed between the base films; An active material formed on each of the base films; And two stiffeners which are bonded to each other and bonded to each other to the back of each of the base films so as to maintain the airtightness of the electrolyte permeated between the active materials.

At this time, the two stiffeners are each provided with a thermal adhesive film so as to surround the base film positioned at the center, and the thermal adhesive films formed on the two stiffeners can be adhered to each other.

At this time, the electrolyte includes a strong corrosive substance, and the thermal adhesive film may include at least one of a plastic paraffin film and a polyolefin film.

At this time, the method of bonding the reinforcing materials to each other may be one or more methods selected from an adhesive application method, a thermal bonding method, a heat welding method, and a welding method.

At this time, the supercapacitor element includes two flexible current collectors; A separator interposed between the current collectors; And an active material layer formed on each of the current collectors.

At this time, two reinforcing materials may be included, which are bonded to each other and bonded to each other so as to maintain the airtightness of the electrolyte permeated between the active materials.

According to a second aspect of the present invention, there is provided a mobile terminal using a supercapacitor which charges electric power for a flash operation through a power supply and performs a flash operation by a light emission request, An LED element emitting light by a current; A flexible thin film type supercapacitor element charged according to the activation of the power supply and supplying the flash current according to a control signal; A control unit for activating the power supply to the supercapacitor device and generating the control signal in response to the light emission request; And a power management unit for controlling a current value supplied from the power source to the supercapacitor element in accordance with the activation of the power supply based on the state of the power source.

At this time, the power management unit may limit a current value flowing into the supercapacitor according to a discharge state of the power source to a predetermined set value.

According to the present invention, it is possible to fabricate a flash module using a flexible thin-film type supercapacitor device which is very thin, flexible, energy-saving, and economical and mass-producible, while maintaining high electrical conductivity and high- Thereby contributing to downsizing of the terminal.

1 is a block diagram of a flash module for a mobile terminal using a supercapacitor device according to the present invention.
2 is a photograph illustrating a flash module for a mobile terminal using a supercapacitor device according to the present invention.
3A is a graph showing a change in terminal voltage value of the supercapacitor element by a switch operation.
3B is a graph showing a current value applied to the LED element by a switch operation.
4 is a block diagram of a mobile terminal having a supercapacitor device according to the present invention.
5A and 5B are views for explaining a manufacturing process of a supercapacitor device according to the present invention.
6A and 6B are tables and photographs showing chemical stability test results according to various embodiments of the base film.
6C is a photograph showing the results of the chemical stability test when the base film is PP.
7 is a photograph of a tackiness test of a current collector formed by plating when the base film is PPS.
FIGS. 8A and 8B are a schematic explanatory view for explaining the process of forming the base film and the pretreatment and current collector when the base film is PP, and a photograph of the adhesion test of the plated current collector.
9 is a schematic view for explaining a process of forming an active material.
10 is a graph showing electrochemical characteristics of a supercapacitor device according to an embodiment of the present invention.
11A and 11B are graphs and electrographic photographs of electrochemical characteristics of a supercapacitor device according to another embodiment of the present invention.
12 to 17 are graphs showing electrochemical characteristics of a supercapacitor device according to still another embodiment of the present invention.

The description of the disclosed technique is merely an example for structural or functional explanation and the scope of the disclosed technology should not be construed as being limited by the embodiments described in the text. That is, the embodiments are to be construed as being variously embodied and having various forms, so that the scope of the disclosed technology should be understood to include equivalents capable of realizing technical ideas.

1 is a block diagram of a flash module for a mobile terminal using a supercapacitor device according to the present invention.

1, a flash module 1000 according to an embodiment of the present invention includes a supercapacitor device 100, a control unit 200, and an LED device 300. The flash module 1000 is used to compensate for insufficient light when photographing a subject using a camera (not shown) of a mobile terminal. In the present invention, 'light emission request' is understood as input of a switching signal such as a shutter operation of a camera .

The supercapacitor element 100 is charged in accordance with the activation operation of the power supply, for example, the operation in which the controller 200 boosts the voltage applied from the power supply 400 and is applied to the supercapacitor element 100, And receives the control signal from the controller 200 to supply the generated flash current to the LED element 300 according to the charged power.

The supercapacitor element 100 according to the present invention is flexible and thin so as to be applicable to a thin-walled mobile terminal, which will be described in more detail in Figs. 5A to 17.

Further, the LED element 300 receives the flash current from the supercapacitor element 100 and emits light. The LED element 300 may be a light emitting diode (LED) element that emits white light. The LED element 300 may include a combination of a blue LED and a yellow light emitting phosphor. A blue LED may emit yellow light and red light A device combining a phosphor, or an element combining ultraviolet LED with blue light emission, yellow light emission and red light emission phosphor can be appropriately selected.

The control unit 200 controls the voltage applied by the power source 400 to be boosted to be applied to the supercapacitor device 100. When receiving a light emission request from the outside, the control unit 200 generates a control signal and supplies the generated control signal to the supercapacitor device 100).

That is, the controller 200 activates a boosting circuit (not shown) for the power source 400 that applies a relatively low voltage to form a path so that the boosted voltage is applied to the supercapacitor element 100, A control signal is generated by sensing that a light emission request is inputted from the outside and a path is formed so that the electric power charged in the supercapacitor device 100 is supplied to the LED device 200 in the form of a flash current have.

2 is a photograph illustrating a flash module for a mobile terminal using a supercapacitor device according to the present invention. 2 is an experimental module for confirming the characteristics of the supercapacitor device 100. In this embodiment, a battery of AA standard is used as the power supply 400, and the light emission request is implemented by the switch 500. [ Meanwhile, as shown in the photograph, it can be understood that the supercapacitor device 100 according to the present invention is implemented in a thin film form.

3A is a graph showing a change in terminal voltage value of the supercapacitor element by a switch operation. The control unit 200 activates a boosting circuit (not shown) to pump the voltage applied from the power source 400 to control the boosting of the voltage applied to the supercapacitor device 100, To be charged.

When the light emission request, that is, the operation of the switch 500, is performed, the charge charged in the supercapacitor 100 is discharged at a time to the LED element 300.

Thereafter, the controller 200 pumps the charge supplied from the power source 400 to charge the super capacitor 100 again. As shown in the figure, after the switch 500 is operated, the charge voltage of the supercapacitor device 100 becomes the initial voltage As shown in Fig.

In the graph, the charging voltage of the supercapacitor element 100 is rapidly recovered by charging after the switch 500 is operated. However, in order to explain the superiority of the charging / discharging characteristics of the supercapacitor element 100, The recharging time of the supercapacitor device 100 is appropriately controlled by the control unit 200 in consideration of the instantaneous current supply capability of the mobile terminal power when applied to an actual mobile terminal.

The mobile terminal power supplies not only the LED flash module but also other modules constituting a mobile terminal such as an AP (application processor) and a display module. When power is rapidly supplied to charge the super capacitor element 100, , The internal terminal voltage of the power source is instantaneously strong due to an increase in the internal resistance of the lithium ion battery, so that malfunction of the mobile terminal may occur or the battery may be discharged.

In order to prevent such erroneous operation, the control unit 200 controls the power supply 400 based on the activation state of the power supply 400, for example, the control unit 200 boosts the voltage applied from the power supply 400 and supplies the boosted power to the supercapacitor device 100 To be applied to the display device.

Specifically, the controller 200 activates a boosting circuit (not shown) for the power source 400 that applies a relatively low voltage to form a path so that the boosted voltage is applied to the supercapacitor device 100, The charge pumping rate is controlled according to the discharge state of the power source 400 so that the current flowing from the power source 400 to the supercapacitor device 100 is kept below the set value.

 That is, the control unit 200 controls the current supplied from the power supply 400 to the supercapacitor device 100 to a set value or less.

3B is a graph showing the flash current supplied from the supercapacitor device 100 to the LED device 300 by the switch operation. 2, the flash current value according to the present invention is not limited to this, and the flash current value of the capacity of the supercapacitor device 100 to be used is about 300 mA, As shown in FIG.

4 is a block diagram of a mobile terminal having a supercapacitor device according to the present invention.

4, a mobile terminal 2000 according to the present invention includes a supercapacitor device 100, a control unit 200, an LED device 300, and a power management unit 600. The flash module 1000 is used to compensate for insufficient light when photographing a subject using a camera (not shown) of a mobile terminal. In the present invention, 'light emission request' is understood as input of a switching signal such as a shutter operation of a camera .

The supercapacitor element 100 is charged in accordance with the activation operation of the power supply, for example, the operation in which the controller 200 boosts the voltage applied from the power supply 400 and is applied to the supercapacitor element 100, And receives the control signal from the controller 200 to supply the generated flash current to the LED element 300 according to the charged power. The super capacitor element 100, the LED element 300, and the control unit 200 have been described in detail in the foregoing, and a detailed description thereof will be omitted.

The power management unit 600 controls the current supplied from the power source 400 to the supercapacitor device 100 based on the state of the power source 400. [ In general, a mobile terminal 2000 uses a lithium ion battery as a power source 400, and a lithium ion battery includes not only an LED element 300 but also other modules of an mobile terminal 2000 such as an AP (application processor) . At this time, when the current is rapidly supplied to charge the super capacitor element 100, the internal resistance of the lithium ion battery increases, and the terminal voltage of the power source 400 is instantaneously decreased. In particular, the supercapacitor device 100 has a high capacity to induce a high inrush current upon charging. When the inrush current causes the output voltage of the power source 400 to instantaneously drop to cause a malfunction in the mobile terminal 2000, It may be judged that it is in the discharge state and the driving of some applications may be restricted.

In order to prevent an instantaneous output voltage drop of the power source 400 due to the inrush current, the power management unit 600 limits the current value flowing into the supercapacitor device 100 to a predetermined value according to the discharge state of the power source 400 do.

For example, when the power source 400 is fully charged (for example, 4.20 V), the power management unit 600 limits the current flowing into the supercapacitor device 100 to the first current value, (For example, 3.40 V), the current value flowing into the supercapacitor device 100 is limited to the second current value, and when the power source 400 is 90% discharged (for example, 3.40 V) The current value flowing into the device 100 can be limited to the third current value. That is, the power management unit 600 limits the current supplied to the supercapacitor device 100 and controls the voltage drop of the output voltage of the power supply 400 to a level that does not hinder the driving of the mobile terminal 2000. The output voltage value and the discharging state of the power supply 400 described above are examples to explain the current control that the power management unit 600 is supplied for charging the super capacitor element 100, And may be variously modified depending on the characteristics of the power source 400 and the characteristics of the supercapacitor device 100 used.

5A and 5B are views for explaining a manufacturing process of a supercapacitor device according to the present invention. 6A and 6B are tables and photographs showing chemical stability test results according to various embodiments of the base film. 6C is a photograph showing the result of the chemical stability test when the base film is PP. 7 is a photograph of a tackiness test of a current collector formed by plating when the base film is PPS. FIGS. 8A and 8B are a schematic explanatory view for explaining the process of forming the base film and the pretreatment and current collector when the base film is PP, and a photograph of the adhesion test of the plated current collector. 9 is a schematic view for explaining a process of forming an active material. 10 is a graph showing electrochemical characteristics of a supercapacitor device according to an embodiment of the present invention. 11A and 11B are graphs and electrographic photographs of electrochemical characteristics of a supercapacitor device according to another embodiment of the present invention. 12 to 17 are graphs showing electrochemical characteristics of a supercapacitor device according to still another embodiment of the present invention.

The super capacitor element 100 of the first embodiment used in the present invention includes a step S110 of forming two base films 110 and a step of forming a current collector 130 on each of the base films 110 A step S130 of forming an active material 150 with graphene oxide in each of the current collectors S120 and S130 and a step S130 of forming a base film 110 including the current collector 130 and the active material 150, (Fig. 5A) including a step S140 of mutually coupling the active materials 150 with each other across the separating film 170 so as to face each other. Hereinafter, for convenience of explanation, the supercapacitor element 100 will be referred to as a "capacitor element".

Here, 'capacitor' in the capacitor element means a lithium-ion capacitor (LiC), an electric double-layer capacitor (EDLC), a pseudocapacitor, a hybrid capacitor, a general electrolytic capacitor, and a common capacitor.

Hereinafter, the contents related to each step will be described in detail.

Preparing base film

First, a base film 110 is provided and the surface is pretreated (S110). The base film 110 is formed of a plastic film including polyphenylene sulfide (PPS), polypropylene (PP) and polyethylene phthalate (PET), and a functional film imparted with an additional function, for example, an aluminum evaporation film Is preferably selected from among the metal-deposited films.

In order to select the base film 110, the base film 110 needs to have flexibility, thermally and chemically stable, to hold the electrolyte stably, and to prevent corrosion due to the electrolyte . The base film is a component for forming a current collector. The reinforcing material is a means for reinforcing and packaging the base film. The base film and the reinforcing material may be the same material. The base film may be used for packaging itself, Can be performed simultaneously. In FIG. 5B, the active material is directly formed on the nickel foil used as the current collector without using the base film, and the PP film is attached as a reinforcing material for packing the current collector with the active material on the back of the nickel foil and the separator and electrolyte. Hereinafter, a capacitor element and a manufacturing method will be described with reference to FIG. 5A. FIG. 5B is the same except that a nickel foil is directly used as a current collector to replace a current collector formed on the base film.

As one example of the base film 110, six films (① polycarbonate - PC - Polycarbonate, ② Silicon - Silicone, ③ Polymethyl methacrylate - PMMA - PoluMethyl Methacrylate, ④ Polyethylene naphthalate - PEN-PolyEhylene Naphthalate, (5) Polyphenylene Sulfide-PolyPhenylene Sultide-PPS, (6) Polyethylene Terephthalate-PET) were selected and tested. The results are shown in FIG. 6A and FIG. 6B, Test results for polypropylene (PP - Polypropylene) are shown.

PPS and PET films were selectively stable only in sulfuric acid. Figure 6b shows the results of chemical stability at room temperature (25 ° C) and 70 ° C As a result, the PPS film has the best chemical stability and it is also preferable to use PC, PEN and PET film when sulfuric acid is used as the electrolyte.

However, the PPS film having the best performance has a disadvantage in low cost mass production because the unit price of the product is rather high. In consideration of this, PP film was selected as a material that can be applied to mass production and satisfying price and performance among films capable of replacing PPS film. PP film is more easily coated with electroless nickel plating film than PPS film There is an advantage that it can be formed. FIG. 2c shows the state of the PP film after the chemical stability test at 6M KOH at 25 ° C and 70 ° C, indicating that the PP film after the chemical stability test is stable.

Then, the surface of the base film 110 is pretreated in order to form a current collector 130 to which a lead wire electrically connected to the outside is connected (S110). The pretreatment of the base film 110 may be performed by a method of roughening or chemically etching the surface of the base film using a tool such as a sandpaper, which is a physical treatment method, or a physical method and a chemical method at the same time.

≪ Example 1 >

When the base film 110 is a PPS film, the surface of the base film 110 is roughened with a sandpaper to coat the electroless nickel film, and the film is ultrasonically washed in ethanol.

≪ Example 2 >

When the base film 110 is a PP film, etching is performed to form an electroless nickel film, and a solution obtained by mixing 400 g / l of chromic acid and 200 ml / l of sulfuric acid as an etching agent is used.

Formation of collector

The process S120 of forming the current collector 130 on the surface of the pretreated base film 110 may be performed by maintaining the high adhesion with the flexible base film 110 while maintaining a high performance, And how it can be done.

≪ Example 3 >

For example, the base film 110 pretreated in Example 1 is immersed in a solution of 5 g of tin chloride (tin chloride (SnCl ₂ ), 20 mL of hydrochloric acid (HCl) and 500 mL of water (H ₂ O)) To sensitize them. Then, the base film 110 is activated by putting it in a solution of palladium (0.125 g of palladium chloride (PbCl ₂ ), 1.25 mL of hydrochloric acid (HCl) and 500 mL of water). Then, when immersed in an electroless nickel plating solution, nickel is plated on the surface of the pretreated base film 110 (S120) to function as a current collector 130.

Here, the electroless composition of nickel plating solution of nickel sulfate (NiSO ₄₎ 25g / l, phosphate susoyi sodium _{(Na 2 HPO 4) 50g /} l, hypophosphite soda _{(NaH 2 PO 2) 25g /} l , and ammonium hydroxide (NH ₄ OH) (pH titration), and the base film 110 contained in the plating solution maintained at a temperature of 70 ° C. (pH 10.5 at this time) for about 10 minutes is taken out of the solution and washed with deionized water. The current collector 130 plated with nickel metal has a thickness of 10 μm, a resistance of 30 to 70 mΩ, and the current collector 130 can maintain very good adhesion with the base film 110. Fig. 7 is a photograph showing a test of adhesion with a tape (3M Scotch magic tape). When the tape was attached and peeled off, nickel hardly appeared and the change in the weight of the film was hardly detected before and after the tape was peeled off .

 <Example 4>

Palladium fine particles were attached to the surface of the base film 110 pretreated in Example 2 through a catalytic process. At this time, the catalyst solution is prepared by mixing 0.25 g / l of palladium chloride, 20 g / l of stannous chloride and 200 ml / l of concentrated hydrochloric acid. Next, when the washed base film 110 is immersed in a solution of sulfuric acid of 150 g / l at a temperature of 50 ° C for 3 minutes, tin (Sn) ions are removed and palladium (Pd) can be activated. After the activated base film 110 is well dried, it is immersed in electroless nickel plating solution at 70 캜 and electroless plating is performed for about 3 minutes. Nickel strike plating is then carried out by electrolytic plating, in which the nickel strike plating solution is made up to contain 240 g / l of nickel sulfate, 45 g / l of nickel chloride and 30 g / l of boric acid. Electroless nickel plated base film 110 was electrolytically plated for 17 minutes at a temperature of 55 캜 and a current of 20 mA / cm ² to complete the electroplating process. According to this embodiment, the current collector 130 made of a nickel layer having a thickness of about 10-12 탆 and a low resistance of about 3-4 mΩ is formed on the surface of the base film 110 with good adhesion to the surface of the base film 110 (See FIG. 8B).

This process is schematically shown in FIG. 8A.

Here, although the current collector 130 is formed by plating, the current collector 130 may be selected from known methods such as a vacuum deposition method, a screen pouring method, a stamping method, and a method using a paste or slurry. In addition, a conductive film including a metal foil, a conductive polymer, a carbon material, and a conductive complex as well as a conductive layer formed by various methods can be applied to the current collector of the present invention.

&Lt; Example 5 >

Although only nickel is described as an embodiment of the metal forming the current collector 130 in the above-described embodiments, the types of the plating metal may be platinum (Pt), silver (Ag), gold (Au) Cu), aluminum (Al), palladium (Pd), and iridium (Ir).

Attaching active material (electrode manufacturing)

&Lt; Example 6 >

It is preferable to form the active material 150 on the current collector 130 in a simple and convenient manner without using an adhesive or the like and to improve the economical efficiency (S130).

That is, graphene oxide is prepared using a Hummer's method, and a graphene oxide solution such as an ink is prepared. For example, a graphene oxide solution is formed on a current collector having a diameter of 2.54 cm After a proper amount is dropped, graphene oxide is deposited on the gold collector surface by hydrothermal evaporation from a hot plate at 90 ° C. Next, the graphene oxide is reduced using light including a camera flash, and the remaining moisture is removed by putting it in an oven at about 200 ° C., and an additional thermal reduction process is performed to form an active material composed of graphene on the current collector 130 (S140). FIG. 9 is a simplified illustration of such an embodiment.

The detailed procedure of the present embodiment is the same as that of the present applicant, 'Grain-based thin film supercapacitor electrode element using oxidized graphene directly and its manufacturing method' (Korean Pat. No. 10-1456477) do.

However, the graphene structure deposited through the hydrothermal evaporation deposition can be induced to form a layer while maintaining the state of mutual bonding without being destroyed or damaged, so that the binding of the active material and the reliability of the product can be improved.

These electrodes have two electrodes corresponding to the positive electrode and the negative electrode.

Capacitor manufacturing

6M KOH is injected into the electrode made of the above process (hereinafter, the "electrode" means a component including the current collector 130 and the active material 150) to complete the half-capacitor device. FIG. 10 is a graph showing the electrochemical characteristics of such a capacitor element (the test is carried out by combining an electrode in an electrode test kit (ECC-Aq, EL-Cell, Germany) and injecting 6M KOH). In Fig. 10, the specific capacitance obtained at 5 mV / s is 178.8 F / g on the half-cell basis and the specific capacitance obtained at 1000 mV / s is 145.4 F / g, which is about 18.7% The equivalent series resistance value (ESR) obtained from the AC-impedance measurement is somewhat low at 0.26 Ω. In addition, there was no reduction in capacity even in a cycle life test of about 100,000 cycles.

On the other hand, unlike the present embodiment, the active material that can be applied to the present invention includes organic and inorganic electrode active materials capable of constituting a known supercapacitor electrode including carbon, for example, a carbon material, a carbon hybrid material, a metal oxide, , Sulfides, conductive polymers, and the like.

&Lt; Example 7 >

The base film 110 made of the PPS film of Example 3 described above is deposited on the nickel current collector 130 by using the hydrothermal evaporation method such as Example 6 and the flash reduction method to reduce the graphene oxide . Next, the moisture was removed by heat treatment at 110 ° C. for 8 hours, and then the electrode was tested in a beaker containing 6 M KOH. FIG. 11 (a) is a photograph showing the state where the active material 150 was formed .

In the cyclic voltammogram of FIG. 11A, the quadrangular shape, which is a typical form of the electric double layer, is maintained up to 30 mV / s. The specific capacity obtained at 5 mV / s is 143.5 F / The equivalent series resistance value (ESR) obtained from the AC-impedance measurement is 1.16 Ω.

&Lt; Example 8 >

5A is a plan view of a base film 110 including a current collector 130 and an active material 150 according to a method similar to the method of forming the capacitor device 100 according to the seventh embodiment of the present invention. (150) are opposed to each other with the separation membrane (170) interposed therebetween (S140).

That is, a heat adhesive (not shown) containing epoxy is thinly applied to the base film exposed around the active material 150 without a reinforcing material, and is sandwiched with the separator 170 therebetween, and then pressurized at room temperature, (100). The finally completed capacitor element 100 has an electrode area of 4 cm 2 (2 cm 2 cm) and a thickness of about 110 μm. The assembled capacitor element 100 is poured into 6M KOH and then vacuum impregnated for about 30 minutes to allow the electrolyte to penetrate the active material 150 well.

FIG. 12 shows the electrochemical characteristics of the capacitor element 100 of the present embodiment. In the cyclic voltammogram, a square shape, which is a typical form of the electric double layer, is maintained up to 30 mV / s. The capacitance obtained at 5mV / s is 123.6F / g based on the half-cell and the registered serial resistance (ESR) obtained from the AC-impedance measurement is 2.21Ω.

&Lt; Example 9 >

The active material 150 is formed on the surface of the current collector 130 by using a nickel foil and the hydrothermal evaporation method such as Example 6 and a flash reduction method. This is for comparison in order to select the active material 150 suitable for the current collector 130, and the capacitor device 100 according to the present embodiment is placed in a beaker containing 6M KOH and subjected to three electrode test 10. In the cyclic voltammogram of FIG. 10, the square shape of a typical shape of the electric double layer is maintained up to 100 mV / s, and the specific capacity obtained at 5 mV / s is 102 F / g based on a half cell, The equivalent series resistance value (ESR) obtained from the AC-impedance measurement is 0.24? Cm 2, and the time constant is 1.27 seconds.

&Lt; Example 10 >

In the case of this embodiment, 95 wt% of graphene powder (Skyspringnanomaterials, inc.), 2.5 wt% of styrene-butadiene rubber (SBR) as a binder and 2.5 wt% of carboxymethylcellulose (CMC) The mixed solution is deposited on the current collector 130 made of nickel foil through hydrothermal evaporation to form the active material 150. FIG. 14 shows a result of the three-electrode test in which the capacitor element 100 is placed in a beaker containing 6 M KOH. In the cyclic voltammogram, the square shape of the electric double layer is maintained up to 500 mV / s, and the non-capacity obtained at 5 mV / s is 57.5 F / g based on the half cell, and the AC impedance The equivalent serial low resistance value (ESR) obtained in the measurement is 0.6? Cm 2 and the time constant is 0.32 sec. The specific capacity was lower than the measured value using reduced graphene oxide as active material, but the improved tackiness with binder showed that the time constant decreased from several seconds to 0.32 seconds.

&Lt; Example 11 >

In the case of this embodiment, a solution obtained by mixing 95 wt% of graphene powder (Skyspring nanomaterials, inc.) And 5.0 wt% of polystyrene with a binder is applied to the nickel foil collector 130 ).

FIG. 15 shows a result of the three electrode test in which the prepared capacitor element 100 is placed in a beaker containing 6M KOH. In the cyclic voltammogram shown in FIG. 15, the quadrangle shape in the form of an electric double layer is maintained up to 500 mV / s, and the specific capacity obtained at 5 mV / s is 55 F / g on the basis of a half cell and the AC impedance ), The equivalent series low resistance value (ESR) is 0.21? Cm 2, and the time constant is 0.04 sec. The non-capacities showed lower values than the values measured when the reduced graphene oxide was used as the active material, but the improved tackiness using the binder seemed to be a factor for lowering the time constant from a few seconds to 0.05 seconds, and using SBR as a binder .

&Lt; Example 12 >

5A schematically illustrates a fabrication process of a capacitor device 100 according to embodiments of the present invention. As described above, the base film 110 is selected as the PP film, and a nickel current collector 130 is formed on the base film 110 by electroplating and electroless plating to a thickness of about 10 탆. Then, a binder is added An active material 150 is deposited on the nickel current collector. The base film 110 to be the two electrodes manufactured in the same manner for assembling the capacitor element 100 is prepared and a film including the PP film is added to the stiffener 193 for external packaging. A heat adhesive film 191 is used to bond the stiffener 193 prepared for the outer packaging and the base film 110 and the heat adhesive film 191 is made of a plastic paraffin film or an olefin- . The auxiliary thermal adhesive 191a is provided for bonding each lead portion and the prepared electrode and the separator 170 are overlapped with each other. Then, the capacitor element 100 is completed through thermal bonding, and finally the completed capacitor element 100 is completed. Has an area of 4 cm 2 (2 cm 2 cm) and a thickness of about 450 m. 6M KOH serving as an electrolyte is injected into the capacitor element 100 and then vacuum-impregnated for about 30 minutes to allow the electrolyte to penetrate the active material well. In this embodiment, the active material 150 is a mixture of 95 wt% of graphene powder and 5 wt% of polystyrene as a binder.

The adhesive, which is an adhesive material used for bonding the device, preferably includes one of acrylate, silicone, epoxy and thermal adhesive.

 FIG. 16 shows the electrochemical characteristics of the capacitor element 100 according to this embodiment. In the cyclic voltammogram of FIG. 16, the square shape of a typical form of the electric double layer is maintained up to 200 mV / s, and the specific capacity obtained at 5 mV / s is 8 F / g on the full- The equivalent serial low resistance value (ESR) obtained from the AC-impedance measurement is 0.5 Ω cm 2 and the time constant is 0.04 sec. Conversion of the non-capacity to half-cell results in lower values than those shown in the half-electrode test at 32 F / g, but 0.04 sec in the time constant, which is not much different from the previous half-electrode test.

On the other hand, in order to form the device, one or a plurality of methods are preferably selected from a bonding method using an adhesive, a thermal bonding method, a heat welding method, and other welding methods.

In the present embodiment, mainly a plastic paraffin film and a polyolefin film were heat-bonded in parallel, and PP films were thermally fused to each other.

Here, an adhesion method capable of stably holding all types of electrolytic solution is preferable. For example, in the case of a lithium battery using an organic electrolyte, if it is assembled using an aluminum pouch, there is no great corrosivity and there is not much trouble in adhesion. However, in the present invention, there is almost no method of stably holding the electrolyte when a corrosive electrolyte such as 6M KOH is used. However, in the present invention, a paraffin film having high hydrophobicity is thermally adhered to the outer surface of the inner electrolyte (Waterproof), and the adhesive force between the base film 110 and the current collector 130 can be maintained by thermally adhering the polyolefin film in a secondary order. Thus, a highly corrosive electrolyte It was possible to stably seal.

This method can be applied not only to the capacitor element but also to the case where the other acid / base must be trapped.

On the other hand, the electrolytes applicable to the present invention include aqueous and non-aqueous (organic, ionic liquid) electrolytes, and the shape of the electrolyte may include liquid, gel, solid type and the like.

On the other hand, the separator that can be applied in the present invention includes a separator made of polyethylene and polypropylene series, nonwoven fabric, and electrolyte.

&Lt; Example 12 >

17 shows the electrochemical characteristics of the capacitor element 100. The active material 150 used contains 95 wt% of graphene powder and 5 wt% of polytetrafluoroethylene (PTFE) as a binder. In the cyclic voltammogram shown in FIG. 14, the square shape, which is a typical shape of the electric double layer, is maintained up to 200 mV / s, and the capacity obtained at 5 mV / s is 11 F / g based on the full- , The equivalent serial low resistance value (ESR) obtained from the AC impedance measurement is 0.47? Cm 2, and the time constant is 0.04 sec. There was a slight increase in capacity compared to devices made using polystyrene binders, but overall performance was similar and visibility was great.

Therefore, according to the present invention, it is possible to provide a simple process which is very thin and flexible while maintaining high electrical conductivity and high bondability, and which does not require an electrochemical etching process even in the manufacturing process, and shortens the heating time in a hydrocarbon atmosphere, And a supercapacitor element according to the method can be provided.

Although the present invention has been fully described by way of example with reference to the accompanying drawings, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. I will understand. Accordingly, the true scope of protection of the disclosed technology should be determined by the appended claims.

1000: Flash module
100: super capacitor element
200:
300: LED element
400: Power supply
500: Switch
600: power management unit

Claims (20)

An LED element emitting light by a flash current;
A flexible thin film type supercapacitor element charged according to the activation of the power supply and supplying the flash current according to a control signal; And
A control unit for activating the power supply to the supercapacitor device and generating the control signal in response to a light emission request;
A flash module for a mobile terminal using a supercapacitor,
The flexible thin-film type supercapacitor element includes:
Two base films having flexibility;
A method of depositing a metal or carbon-containing conductor on the surface of the base film after the surface treatment of the base film by one or more of plating, vacuum deposition, screen printing, and stamping, Collecting house;
An active material layer formed by coating a graphene oxide solution on the current collector, heating the same, irradiating the graphene oxide solution, and then performing heat treatment; And
Wherein the two base films are disposed so that the active material layers are opposed to each other,
Wherein the two base films are adhered to each other by a thermal adhesive applied to surround the active material layer on the periphery of the two base films.
delete delete delete The method according to claim 1,
Wherein the base film is selected from a polyphenylene sulfide (PPS) film, a polypropylene (PP) film, a polycarbonate (PC) film, a polyethylene naphthalate (PEN) film, and a polyethylene terephthalate (PET) Flash module for mobile terminal using.
The method according to claim 1,
Wherein the base film is a film on which a metal containing aluminum is deposited.
delete The method according to claim 1,
Wherein the current collector comprises at least one selected from the group consisting of Ni, Pt, Ag, Au, Cu, Al, Pd, Wherein the flash memory module is a metal layer.
The method according to claim 1,
Further comprising an electrolyte permeating the active material layer,
The electrolyte is an aqueous electrolyte or a non-aqueous (organic, ionic liquid) electrolyte,
Wherein the shape of the electrolyte is one of liquid, gel, and solid.
delete The method according to claim 1,
Wherein the thermal adhesive comprises at least one selected from the group consisting of acrylate, silicone, and epoxy.
The method according to claim 1,
Wherein the separation membrane is one selected from the group consisting of polyethylene (PE), polypropylene (PP) film, nonwoven fabric, and electrolyte-integrated separation membrane.
The method according to claim 1,
The supercapacitor element includes:
And two stiffeners joined to the back of each of the base films and bonded to each other. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
14. The method of claim 13,
Wherein the two stiffeners are each provided with a thermal adhesive film so as to surround the base film positioned in the center and the thermal adhesive films formed on the two stiffeners are bonded to each other.
15. The method of claim 14,
Further comprising an electrolyte permeating the active material layer,
The electrolyte contains a strong corrosive substance,
Wherein the thermal adhesive film comprises at least one of a plastic paraffin film and a polyolefin film.
15. The method of claim 14,
Wherein the method of bonding the reinforcing materials to each other is one or more selected from the group consisting of an adhesive method, a thermal bonding method, a thermal fusion method, and a welding method.
delete delete An LED element emitting light by a flash current;
A flexible thin film type supercapacitor element charged according to the activation of the power supply and supplying the flash current according to a control signal;
A control unit for activating the power supply to the supercapacitor device and generating the control signal in response to the light emission request; And
A power management unit for controlling a current value supplied from the power source to the supercapacitor element according to the activation of the power supply based on the state of the power source;
The superconductor of claim 1,
The flexible thin-film type supercapacitor element includes:
Two base films having flexibility;
A method of depositing a metal or carbon-containing conductor on the surface of the base film after the surface treatment of the base film by one or more of plating, vacuum deposition, screen printing, and stamping, Collecting house;
An active material layer formed by coating a graphene oxide solution on the current collector, heating the same, irradiating the graphene oxide solution, and then performing heat treatment; And
Wherein the two base films are disposed so that the active material layers are opposed to each other,
Wherein the two base films are adhered to each other by a thermal adhesive applied to surround the active material layer on the periphery of the two base films.
The method of claim 19,
Wherein the power management unit limits a current flowing into the supercapacitor according to a discharge state of the power supply to a predetermined set value.

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