KR101391136B1 - Method for manufacturing graphite film electro-deposited metal oxide for supercapacitor electrode and supercapacitor comprising the same - Google Patents
Method for manufacturing graphite film electro-deposited metal oxide for supercapacitor electrode and supercapacitor comprising the same Download PDFInfo
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- KR101391136B1 KR101391136B1 KR1020120052519A KR20120052519A KR101391136B1 KR 101391136 B1 KR101391136 B1 KR 101391136B1 KR 1020120052519 A KR1020120052519 A KR 1020120052519A KR 20120052519 A KR20120052519 A KR 20120052519A KR 101391136 B1 KR101391136 B1 KR 101391136B1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a method of manufacturing an electrode using a conventional conductive agent and a binder, and a method of manufacturing a metal oxide / graphite electrode for a supercapacitor, which comprises electrochemically depositing a metal oxide layer on a graphite. Alternatively, the metal oxide / graphite composite electrode can be directly manufactured by electrodeposition of a metal oxide directly on the graphite, and the electrode can be used as an electrode, thereby simplifying the manufacturing process and reducing the process cost. Also, it is possible to manufacture electrodes with improved performance by variously controlling the kind, size and thickness of the metal oxide electrodeposited on the graphite electrode, and the present invention can be applied to various fields such as a super capacitor and a secondary battery.
Description
The present invention relates to a method of manufacturing an electrode for a supercapacitor, and more particularly, to a method of manufacturing a metal oxide / graphite electrode by electrodepositing a metal oxide directly on a graphite sheet by an electrochemical method and using the electrode as an electrode.
Electrochemical capacitors, called supercapacitors or ultracapacitors, have higher energy densities than conventional capacitors, higher power densities than secondary cells, and much better than other energy storage devices Cycle life characteristics, and the like.
The super capacitor includes an electric double layer capacitor (EDLC) using activated carbon as an electrode material, a conductive polymer such as polyaniline and polypyrrole, a conductive polymer such as RuO 2 , MnO 2 (Mn-Ni, Mn-Co, etc.) and the like are used as an electrode material, and a pseudo-capacitor.
Currently, electric double layer capacitors (EDLC) use an activated carbon material as a porous structure. Activated carbon has a large specific surface area and uniform pores and high capacitance. In addition, it has an advantage of having low equivalent series resistance (ESR) due to high electrical conductivity and high ion diffusion rate and stable in a wide potential range. However, due to the limitation of the storage capacity, the low energy density acts as a limiting factor. As an alternative to the EDLC, pseudo-capacitors using metal oxides with a storage capacity three to four times larger than EDLC are actively studied have.
As a method for producing a metal oxide as an electrode material of a pseudo capacitor, there has been known a conventional method of preparing by coprecipitation and freeze-drying, a method of sputtering on nano pores of an alumina template, a method of coating a conductive polymer A method of manufacturing a metal oxide, or a method of manufacturing using a carbon nanotube nanocomposite material.
As such prior arts, Korean Patent Registration No. 10-1064299 discloses a nickel-manganese bicomponent composite electrode material prepared by chemical coagulation and freeze-drying, and Korean Patent No. 10-1102982 discloses a nickel- There is disclosed a method for producing a metal oxide by coating a conductive polymer using a chemical polymerization method. Also, non-patent documents Yi-Shiun et al., Electrochemical and Solid-State Letters, 6 (10), A210-A213 (2003); A method for manufacturing a supercapacitor electrode using a metal oxide is disclosed in, for example, Chi-Chang Hu et al., Electrochemical and Solid-State Letters, 5 (3) A43-A46 (2002)
Since the electrode material according to the above method is in a powder state, it is always mixed with a binder for adhesion with a carbon-based conductive agent and is attached to an aluminum foil to manufacture an electrode for a supercapacitor, The manufacturing cost is increased, which is an inefficient problem. Also, the electrochemical electrodeposition method of manganese oxide, which has been studied previously, is still inefficient because the electrodes used in this process are expensive materials such as platinum, nickel foil, and carbon nanotube.
[Prior Art Literature]
[Patent Literature]
Korean Patent Registration No. 10-1064299 (published on May 26, 2010)
Korean Patent Registration No. 10-1102982 (Published Feb., 2011)
[Non-Patent Document]
Yi-Shiun et al., Electrochemical and Solid-State Letters, 6 (10), A210-A213 (2003);
Chi-Chang Hu et al., Electrochemical and Solid-State Letters, 5 (3) A43-A46 (2002)
Accordingly, a problem to be solved by the present invention is to use a graphite sheet as an electrode material, electrodeposition the metal oxide by an electrochemical method, and directly use the electrode as an electrode, And to provide a method for manufacturing the improved metal oxide / graphite composite electrode.
In order to solve the above problems,
And electrochemically depositing a metal oxide layer on the graphite. The present invention also provides a method of manufacturing a metal oxide / graphite electrode for a supercapacitor.
According to an embodiment of the present invention, the electrochemical electrodepositing step includes the steps of: (a) using Ag / AgCl as a reference electrode in a bath containing a metal oxide precursor solution; To form a three-electrode system bath; And
(b) applying a power of -1.2 V for 30 to 180 seconds in the bath to electrodeposit the metal oxide layer directly on the graphite.
According to another embodiment of the present invention, the metal oxide is selected from the group consisting of nickel oxide, cobalt oxide, iron oxide, magnesium oxide, copper oxide, zinc oxide, indium oxide, ruthenium oxide, vanadium oxide, iridium oxide and lead oxide And may be one or more selected metal oxides.
According to another embodiment of the present invention, the metal oxide precursor solution is an aqueous solution containing manganese acetate (Mn (CH 3 COO) 2 .4H 2 O) and nickel chloride (NiCl 2 .6H 2 O) Nickel molar ratio may be between 1: 1 and 1: 3.
According to another embodiment of the present invention, before the electrochemical electrodeposition step, pre-treating the graphite sheet may further include:
The pretreatment step may include rubbing the graphite sheet with silicon carbide paper (SiC paper) to increase the roughness of the surface, chemically etching it by immersing it in sulfuric acid, and immersing it in a methanol solution to remove impurities.
According to another embodiment of the present invention, the method may further include crystallizing the metal oxide by heat-treating the metal oxide electrodeposited on the graphite sheet after the electrochemical electrodeposition step,
The heat treatment may be a heat treatment at 200-300 ° C for 2-4 hours.
In order to solve the above problems,
The present invention also provides a super capacitor including the metal oxide / graphite electrode, which is manufactured according to the above-described method.
According to the present invention, a metal oxide / graphite composite electrode is manufactured by directly depositing a metal oxide on a graphite, unlike the conventional method of manufacturing an electrode using a conductive agent and a binder, and the electrode can be used as an electrode. And at the same time, reduces the cost of the process. Also, it is possible to manufacture electrodes with improved performance by variously controlling the kind, size and thickness of the metal oxide electrodeposited on the graphite electrode, and the present invention can be applied to various fields such as a super capacitor and a secondary battery.
FIG. 1 is a conceptual diagram showing a structure of a bath and an electrode for electrodeposition of manganese-nickel oxide directly on a graphite electrode according to an embodiment of the present invention.
2 is a SEM image of manganese-nickel oxide electrodeposited on a graphite sheet produced in a bath having a nickel / manganese molar ratio of 2: 1 with an electrochemical deposition time of 60 seconds according to an embodiment of the present invention.
FIG. 3A is an SEM image of the electrodeposited manganese-nickel metal oxide according to the present invention before heat treatment, and FIG. 3B is an SEM image after heat treatment.
FIG. 4 is a graph of charge / discharge for an electrode manufactured by varying the electrochemical deposition time with a molar ratio of manganese and nickel of 1: 2 according to one embodiment of the present invention.
FIG. 5 is a graph showing a capacitance measurement value for an electrode manufactured at a molar ratio of manganese and nickel of 1: 2 according to an embodiment of the present invention and having different electrochemical deposition times. FIG.
Hereinafter, the present invention will be described in more detail.
The present invention relates to a method for directly depositing a metal oxide, particularly a manganese-nickel metal oxide, on a carbon-based substrate, in particular, a graphite sheet, using an electrochemical method to form a supercapacitor The present invention provides a method for manufacturing an electrode for use in a simple process in a short time.
The present invention is characterized in that the process steps are drastically reduced in the method of manufacturing the electrode by preparing the conventional metal oxide as the powder particle, thereby reducing the process cost.
In addition, the metal oxide can be formed in a desired size and thickness by adjusting manufacturing process parameters such as electrochemical deposition time, metal concentration of metal oxide precursor, and heat treatment time of metal oxide crystallization.
The method for preparing a metal oxide / graphite electrode for a supercapacitor according to the present invention comprises the steps of: (i) preparing a bath containing a precursor solution in which a molar ratio of nickel and manganese capable of electrodepositing a metal oxide, particularly a manganese- (Iii) electrochemically electrodepositing the working electrode and the counter electrode, respectively, by varying the size of the pretreated graphite sheet, (iv) electroplating the electrodeposited graphite sheet, And a step of crystallizing the electrodeposited metal oxide by heat treatment.
The present invention can control the performance of the supercapacitor electrode by adjusting the size of the metal oxide particles to be electrodeposited and the thickness of the metal oxide layer by adjusting process parameters such as dislocation, electrodeposition time, and heat treatment time used for electrodeposition .
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It will be clear to those who have knowledge.
<Examples>
Example 1. Preparation of manganese-nickel oxide / graphite electrode
(1) Preparation of graphite sheet
The graphite sheet to be used for the working electrode and the counter electrode was cut out in advance for different sizes for the working electrode and the counter electrode. Each sheet was subjected to the following pretreatment process.
First, the surface roughness of the sheet was increased by rubbing with SiC paper (silicon carbide paper) and physical polishing. Then, the surface was chemically etched by immersing in 20 wt% sulfuric acid for 20 seconds and immediately immersed in a 2 M methanol solution for 20 seconds to remove micro-level defects and impurities. After removing from the methanol, the surface was thoroughly rinsed with distilled water, and then dried in an oven at 65 ° C for 6 hours to remove moisture. Before the electrodeposition, the sheet was prepared to dryness and avoided exposure to the air as much as possible.
(2) Preparation of manganese-nickel aqueous solution
Manganese acetate (Mn (CH 3 COO) 2 · 4H 2 O) and nickel chloride (NiCl 2 · 6H 2 O) were used as precursors for the preparation of Mn-Ni oxide electrodes for supercapacitors. A manganese-nickel aqueous solution was prepared so that the molar ratio of manganese to nickel was 1: 2.
(3) Electrodeposition of manganese-nickel oxide on the graphite sheet
A prepared graphite sheet having a size smaller than that of the working electrode was connected to a counter electrode having a size three times larger than that of the working electrode, and the Ag / AgCl electrode was set as a reference electrode in the bath. The manganese-nickel oxide was electrodeposited on the graphite sheet by a constant potentiostatic method. That is, in the potentiostatic mode, -1.2 V was applied and the time was changed to 30, 60, 120, and 180 seconds to electrodeposition while controlling the amount of manganese-nickel oxide electrodeposited.
According to the constant potential electrodeposition method, it is possible to control the electrodeposition amount by fixing the electric potential and the time, and accordingly, an electrode having a desired capacitance in a manganese-nickel bath can be manufactured.
(4) Heat treatment step
After electrodeposition of the manganese-nickel oxide according to (3), the surface was washed with distilled water and annealed at 250 ° C for 3 hours to remove water and crystallize the oxide.
2 is an SEM image of a manganese-nickel oxide electrodeposited on a graphite sheet produced in a bath having a nickel / manganese molar ratio of 2: 1 with an electrochemical deposition time of 60 seconds according to the above embodiment, and FIG. 2 As can be seen, the manganese-nickel metal oxide according to the present invention is crystallized to have a fiber shape and its length is about 60-100 nm.
Experimental Example 2. Confirmation of crystallization change of oxide layer before and after heat treatment
FIG. 3A is an SEM image of the electrodeposited manganese-nickel metal oxide before heat treatment, FIG. 3B is an SEM image after heat treatment, which shows the shape of the metal oxide before the heat treatment but before the crystallization, And crystallization occurs after the heat treatment, so that a metal oxide crystal having a fiber shape can be confirmed on the surface.
EXPERIMENTAL EXAMPLE 2 Charging / discharging test
The charge and discharge tests were carried out in a bath consisting of a three electrode system. Ag / AgCl electrode and platinum electrode were used as the reference electrode and the counter electrode, respectively. 0.5 M Na 2 SO 4 The prepared nickel-manganese electrode was first fully discharged until it reached 0 V and then charged at a current of 10 mA in a potential range of 0 to 0.85 V (vs. Ag / AgCl) I was completely discharged with mA. FIG. 4 is a graph showing the results of charge and discharge tests for electrodes prepared by different electrochemical deposition times in a 1: 2 molar ratio of manganese and nickel. It can be seen that the charging and discharging behaviors are also different as the capacitances depend on the electrodeposition time.
Experimental Example 3. CV Experiment
In order to calculate the capacitance of the electrode manufactured according to the present invention, 0.5 M Na 2 SO 4 Ag / AgCl was used as a reference electrode in the solution, and a platinum electrode of 2 × 2 cm 2 was used as a counter electrode by using a counter electrode. The CV curve was obtained by applying a scanning speed of 20 ㎷ / s in the range of -0.2 ~ 1.0 V. The capacitance was measured using the equation C = I / (dV / dt). As shown in FIG. 5, the capacitance of the electrode manufactured according to the present invention has various capacitance values of 490-270 F / g depending on the electrodeposition time of Example 1- (3).
Claims (7)
And a step of crystallizing the manganese-nickel composite oxide by heat-treating the manganese-nickel composite oxide electrodeposited on the graphite sheet,
Wherein the electrochemical electrodeposition step comprises the steps of: (a) using Ag / AgCl as a reference electrode in a bath containing a solution of a manganese-nickel composite oxide precursor, and connecting a graphite sheet to a working electrode and a counter electrode, Constituting a bath; And
(b) applying a power of -1.2 V for 30 to 180 seconds in the bath to directly electrodeposit the manganese-nickel complex oxide on the graphite,
Wherein the heat treatment is performed at 200-300 캜 for 2-4 hours. The method of manufacturing a metal oxide / graphite electrode for a supercapacitor according to claim 1,
Wherein the metal oxide precursor solution is an aqueous solution containing manganese acetate (Mn (CH 3 COO) 2 .6H 2 O) and nickel chloride (NiCl 2 .4H 2 O), wherein the molar ratio of manganese to nickel is 1: 3. The method for producing a metal oxide / graphite electrode for a supercapacitor according to claim 1,
Further comprising pretreating the graphite sheet prior to the electrochemical electrodeposition step,
Wherein the pretreatment step comprises rubbing the graphite sheet with silicon carbide paper (SiC paper) to increase the surface roughness, then immersing it in sulfuric acid, chemically etching it, and immersing it in a methanol solution to remove impurities. Method for the manufacture of metal oxide / graphite electrodes for capacitors.
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| CN103871752B (en) * | 2014-03-19 | 2016-08-31 | 山东大学 | A kind of oxidation cuprio asymmetric type supercapacitor and preparation method thereof |
| CN105420794B (en) * | 2015-11-13 | 2018-01-26 | 上海应用技术学院 | A kind of preparation method of graphene/ferriferrous oxide composite material |
| CN106847546B (en) * | 2017-04-05 | 2019-01-18 | 苏州海凌达电子科技有限公司 | A kind of preparation method of porous vanadic anhydride super capacitor material |
| CN107104004A (en) * | 2017-05-22 | 2017-08-29 | 华北电力大学（保定） | A kind of flexible electrode, its preparation method and ultracapacitor |
| KR102207729B1 (en) * | 2018-12-19 | 2021-01-26 | 성균관대학교산학협력단 | Method for manufacturing printed super capacitor for nfc tag and method for manufacturing nfc tag including the printed super capacitor |
| CN113594448A (en) * | 2021-07-05 | 2021-11-02 | 武汉科技大学 | Preparation method for directly constructing sulfur-doped iron-cobalt-nickel ternary oxide nanotube, product and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20050048173A (en) * | 2003-11-19 | 2005-05-24 | 한국과학기술연구원 | Method for preparing thin film of ruthenium oxide using electrodeposition |
| JP2009510767A (en) * | 2005-09-30 | 2009-03-12 | ウイスコンシン アラムナイ リサーチ フオンデーシヨン | Electrochemical double layer capacitor using organosilicon electrolyte |
| KR20090121143A (en) * | 2008-05-21 | 2009-11-25 | 주식회사 에이엠오 | Electrode of supercapacitor manufactured by electrospinning and method for manufacturing the same |
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| KR20050048173A (en) * | 2003-11-19 | 2005-05-24 | 한국과학기술연구원 | Method for preparing thin film of ruthenium oxide using electrodeposition |
| JP2009510767A (en) * | 2005-09-30 | 2009-03-12 | ウイスコンシン アラムナイ リサーチ フオンデーシヨン | Electrochemical double layer capacitor using organosilicon electrolyte |
| KR20090121143A (en) * | 2008-05-21 | 2009-11-25 | 주식회사 에이엠오 | Electrode of supercapacitor manufactured by electrospinning and method for manufacturing the same |
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