KR100550208B1 - Fabrication Method of Nano Complex Electrode Comprising Electrode Material Joined with Solid Electrolyte for Thin Film Battery - Google Patents

Abstract

The present invention provides a method of manufacturing a nanocomposite electrode in which an electrode material and a solid electrolyte are integrated by coping with an electrode material and a solid electrolyte as a means for obtaining a high capacity characteristic by improving the ion conductivity of the electrode. do.

Description

Fabrication Method of Nano Complex Electrode Comprising Electrode Material Joined with Solid Electrolyte for Thin Film Battery}             

1 is a schematic configuration diagram of an RF magnetron cottering equipment designed for couttering a solid electrolyte and an electrode material as an embodiment according to the present invention;

2A and 2B are X-ray patterns and XPS structural analysis results of a nanocomposite electrode structure constituting a thin film battery integrated with a solid electrolyte and an electrode material according to a preferred embodiment of the present invention.

Figure 3 is a result photo of the electron transmission microscope according to the particle size of the nanocomposite electrode when the solid electrolyte in accordance with the preferred embodiment of the present invention

4 is a result graph of capacity comparison between a thin film battery having a nanocomposite electrode and a general thin film battery according to a preferred embodiment of the present invention.

5 is a graph showing the results of stability and lifetime evaluation between a thin film battery having a nanocomposite electrode and a general thin film battery according to a preferred embodiment of the present invention.

The present invention relates to a method for manufacturing an electrode for a thin film battery, and more particularly, to a method for manufacturing a nanocomposite electrode which can obtain a high capacity characteristic by integrating a solid electrolyte with an electrode material to improve ion conductivity of the electrode.

In general, thin film batteries produce power by thinning battery components and converting chemical energy into electrical energy, but have a low capacity due to low ion conductivity. The battery consists of a negative electrode, a positive electrode, and an electrolyte, and in the case of a thin film battery, a solid electrolyte is used instead of a liquid solution. Such solid electrolytes include LIPON, Ta ₂ O ₅ , and the like, which are separated from the electrode and used as separate layers.

Conventionally, the capacity has been improved through a method using a binary material in order to increase the efficiency of the electrode. For example, a method of achieving high capacity by doping silicon oxide to tin oxide as a cathode material. However, as electric devices are increasingly high in capacity and high in efficiency, high power is required, and in addition to the existing single and binary systems, ternary systems are required for high efficiency.

The present invention has been made to solve the problems of the prior art, the object of the present invention is to provide a method of manufacturing a nanocomposite electrode for a thin film battery having a high capacity characteristics by integrating a solid electrolyte with an electrode material to improve the ion conductivity of the electrode. Is in.

In order to achieve the above object, the present invention provides a method for manufacturing a nanocomposite electrode in which the electrode material and the solid electrolyte are integrated by coping with the electrode material and the solid electrolyte as a target.

The term 'electrode material' refers to a material made of a cathode or an anode in a conventional thin film battery, and includes a material suitably formed as a target for sputtering.

EMBODIMENT OF THE INVENTION Hereinafter, the content of this invention is demonstrated in detail with drawing.

The configuration of the apparatus for carrying out the invention is as schematically shown in FIG. In the case of the apparatus used for co-sputtering, referring to FIG. 1, two or more sputtering guns are mounted on the basis of the existing basic sputtering apparatus, instead of using one sputtering gun. In accordance with a preferred embodiment of the present invention, a co-sputtering process is performed through a process called co-deposition by providing respective RF powers to an electrode material and a solid electrolyte as target materials in the conventional RF magnetron sputtering apparatus. Show the deposition process.

Referring to FIG. 1, the target 1 and the target 2 are mounted with an electrode material and a solid electrolyte, respectively, and the target gun positioned at both sides thereof is inclined about 20 to 80 degrees with respect to the substrate. When RF power is supplied to target 1 and target 2, the simultaneous deposition of the two materials proceeds simultaneously with the formation of plasma.

Examples of electrode materials usable for the production of nanocomposite electrodes do not require any particular limitation, and include Sn-based, Si, SiSn, and SiO, including Sn, SnO, SnO ₂ , SnSi, SnFe, SnO ₂ SiO ₂ , and the like. ₂ , Si-based containing SiO ₂ SnO ₂ , SiO ₂ Fe and the like, V-based including V ₂ O ₅ , V ₂ OPt, V ₂ O ₅ MnO ₂ , VO _x , LiCoO ₂ , LiMnO ₂ and the like In addition to Li-based materials, Mn-based and Co-based materials may be used.

In addition, the solid electrolyte is a material capable of passing a current in a solid state by the movement of ions (cations or anions), and examples thereof do not require special limitations, and LIPON, Ta ₂ O ₅ , Li _3.6 Si _0.6 P _0.4 O ₄ and the like.

The deposition ratio of the electrode material and the solid electrolyte is different depending on the RF power or deposition time applied to the target material, and the distance between the target and the substrate. Preferably, about 0.1-0.4 are good.

RF magnetron sputtering does not require any particular limitation, but can be achieved through the following conditions.

(1) power: 10W ~ 120W, (2) gas type: Ar, Ar: O2, N2

(3) Gas flow rate: 10 to 60 SCCM, preferably 40 SCCM

(4) Deposition time: depending on the material and thickness, for metals: 10 minutes to 1 hour, for oxides: 30 minutes to 6 hours

Referring to the contents of the present invention as a preferred embodiment, RF magnetron sputtering is an electrode material (target 1: Sn) and a solid electrolyte (target 2: Ta ₂ O ₅ ) to each other using a device as shown in FIG. After mounting, the power of the target can be achieved by adjusting the target 1 to 50W and the target 2 to 20W, respectively, with appropriate time. At this time, the basic pressure during sputtering is 5 * 10 ^-6 torr, the operating pressure is 5 * 10 ^-3 torr, and an argon gas atmosphere of 40 SCCM was used at room temperature in the air. In the deposition process, a silicon substrate was used, and sputtering was performed with the same power and time on one electrode material Sn with a single electrode to perform a comparative experiment.

The nanocomposite electrode manufactured by the above embodiment may be uniformly formed to a thickness of about several hundred μm in several nm. When the negative electrode material is composed of tin metal as described above, the theoretical capacity has 4.4 capacity per molecule, but in the case of a thin film battery composed only of electrode material, it shows 3.0 capacity per molecule, and according to the present invention, Ta ₂ O is a solid electrolyte. _In the case of coping ₅ with the electrode material, a high capacity close to 4.1 theoretical capacity per molecule was obtained (30% performance improvement).

In addition, while general RF magnetron sputtering has a fixed composition of a thin film electrode but cannot have a nano structure, the method of the present invention can produce an electrode having a nano structure with variously controlled compositions. At this time, the adjustment of the composition may be performed by adjusting the power of the target, gas pressure, the distance between the gun and the like.

Structural and Component Analysis

Figure 2a is a photograph of the result confirmed by XRD that the state of the polycrystalline electrode (Sn) is present on the amorphous solid electrolyte base for the electrode obtained through the preferred embodiment. The XRD pattern of the nanocomposite electrode (Sn-Ta ₂ O ₅ ) as well as the single electrode (Sn) is described in JCPDS cards No. Consistent with 04-0673. In addition, since no peak of the XRD pattern is observed, it can be confirmed that the solid electrolyte (Sn-Ta ₂ O ₅ ) base is amorphous. Therefore, it can be confirmed from these results that a nanocomposite electrode (Sn-Ta ₂ O ₅ ) having an amorphous solid electrolyte base and a nanostructured electrode (Sn) is formed on one electrode.

Figure 2b is a structural analysis of the XPS according to this, not only can know the exact composition of the electrode, it can be confirmed that the correct electrode structure and the solid electrolyte is in the amorphous oxide state. In addition, it was confirmed that the results were consistent with the XRD analysis through the three-dimensional XPS results, and no oxide peaks such as tin oxide were observed to confirm that nanocomposite electrodes having the correct composition were obtained.

Electron microscopy analysis

3 illustrates a nanocomposite electrode (Sn-Ta ₂ O ₅ ) formed of an electrode material (Sn: dark region) and an amorphous solid electrolyte (Ta ₂ O ₅ : bright region). This confirms that particles having an average size of ˜25 nm are well dispersed. Furthermore, as a result of observing through the TEM image, it was confirmed that the electrode was embedded in the amorphous solid electrolyte.

From the above facts, the nanocomposite electrode of the present invention is expected to be able to help the quick and easy movement of lithium during charging and discharging in a lithium secondary battery, and is expected to be able to manufacture a high performance thin film battery.

Performance evaluation

4 shows a nanocomposite electrode (Li / Sn-Ta ₂ O ₅ ) and a single electrode (Li / Sn cells) as a control, measured at a current density of 20 A / cm ² with a voltage range of 0.2 to 1.8 V. Shows the results of charge and discharge experiments. In the case of nanocomposite electrodes, there is a clear difference in capacitance during the first cycle compared to a single electrode. That is, in the case of a single electrode, three lithium per molecule reacted and about half were removed during charging. In the case of the nanocomposite electrode according to the present invention, 4.1 lithium reacted. Therefore, it was confirmed from this fact that the nanocomposite electrode according to the present invention has a much higher performance than the single electrode. This is due to the easy access of lithium ions by coping the solid electrolyte with the electrode material, and also due to the significantly increased reaction site of the nano-level electrode. From the above fact, it can be seen that the thin film battery including the nanocomposite electrode according to the present invention can obtain high efficiency due to high performance when applied to various electromechanical devices.

Cycle Characteristic Evaluation

In order to further elucidate the electrochemical characteristics of the nanocomposite electrode according to the present invention, the cycle characteristics were evaluated and the data with the single electrode were compared. It can be observed from the results of FIG. 5 that the nanocomposite electrode according to the present invention exhibits excellent initial stability as well as excellent stability compared to a single electrode.

According to the present invention, it is possible to manufacture a thin film battery having high capacity by improving the ion conductivity of the electrode by integrating the solid electrolyte with the electrode material by using the couttering method.

Claims (4)

A method of manufacturing a composite nano-electrode in which an electrode and a solid electrolyte are integrated by coping with an electrode material and a solid electrolyte as a target. The method of claim 1, wherein the electrode is selected from Sn-based, Si-based, V-based, Li-based, Mn-based, or Co-based materials. The method of claim 1, wherein the solid electrolyte is selected from LIPON, Ta ₂ O ₅ , Li _3.6 Si _0.6 P _0.4 O ₄ . The method according to claim 1, wherein the angle of the target is formed so as to be positioned between 20 and 80 degrees with the substrate.

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