JP2015048302A - Method for synthesizing graphene-based nano composite material, and graphene-based nano composite material synthesized using the method - Google Patents

Method for synthesizing graphene-based nano composite material, and graphene-based nano composite material synthesized using the method Download PDF

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JP2015048302A
JP2015048302A JP2014174305A JP2014174305A JP2015048302A JP 2015048302 A JP2015048302 A JP 2015048302A JP 2014174305 A JP2014174305 A JP 2014174305A JP 2014174305 A JP2014174305 A JP 2014174305A JP 2015048302 A JP2015048302 A JP 2015048302A
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graphene
metal oxide
oxide
fepo
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キム、カン−ボム
Kwangbum Kim
チェガル、チョン−ピル
Jongpil Jegal
キム、ヒョン−ギョン
Hyunkyung Kim
ユン、スン−ボム
Seungbum Yoon
キム、ミョン−ソン
Myeongseong Kim
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Industry Academic Cooperation Foundation of Yonsei University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/28—Solid content in solvents
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of easily forming a nano composite material from a metal oxide and a graphene material in a short time.SOLUTION: The method comprises: a step in which a solution into which graphene oxide is dispersed is provided; a step in which a raw material substance for forming a metal oxide is added to the solution; and a step in which a nano composite material in which the metal oxide is formed on at least one side of the graphene surface reduced using an oxidation-reduction reaction between the graphene oxide and the raw material substance for forming a metal oxide is formed, and the reduction potential of the metal oxide is 1.0 V or lower, where the metal oxide includes one selected from the group consisting of FePO, FeOand SnO.

Description

本発明は、グラフェン系ナノ複合材料の合成方法、より詳しくは、酸化還元反応を用いてグラフェン系ナノ複合材料を高速で合成する方法、及び該方法を用いて合成されたグラフェン系ナノ複合材料に関する。   The present invention relates to a method for synthesizing a graphene-based nanocomposite material, and more particularly, to a method for synthesizing a graphene-based nanocomposite material at high speed using an oxidation-reduction reaction, and a graphene-based nanocomposite material synthesized using the method .

グラフェンは、高い電気伝導度（〜１０6Ｓｃｍ-1）及び広い比表面積（２６３０ｍ2ｇ-1）などの既存の炭材料料に比べて遥かに優れた固有の物性のため、未来産業の根幹になる材料として学界や産業界などの多岐にわたる分野において注目を集めている。また、グラフェン系ナノ複合材料は、グラフェンの優れた物性によって既存の材料に比べて遥かに優れた特性を示し、触媒、電子材料、エネルギー材料、生体医学材料などの多岐にわたる分野において既存の材料に代わる未来の材料として大いに注目を集めている。したがって、全世界の多くの研究グループが優れた性能を示すグラフェン系ナノ複合材料の合成技術の確保に熱をあげている。 Graphene is the foundation of the future industry because of its inherent properties far superior to existing charcoal materials such as high electrical conductivity (~ 10 6 Scm -1 ) and large specific surface area (2630 m 2 g -1 ). As a material to become, has attracted attention in various fields such as academia and industry. In addition, graphene-based nanocomposites exhibit far superior properties compared to existing materials due to the excellent physical properties of graphene, making them an existing material in a wide range of fields such as catalysts, electronic materials, energy materials, and biomedical materials. It has attracted much attention as an alternative material for the future. Therefore, many research groups around the world are eager to secure the synthesis technology of graphene-based nanocomposites with excellent performance.

ナノ複合材料のうちのグラフェンの優れた物性を利用するためには、グラフェンと活物質間の均一な分布が何より重要であるが、このためにグラフェンの表面に活物質の不均質核生成（ｈｅｔｅｒｏｇｅｎｅｏｕｓ ｎｕｃｌｅａｔｉｏｎ）を導入した方法が最も確実な方法として台頭されており、これを実現するための多くの研究が鋭意進められてきた。既存に報告された研究では、均一な分布を有するグラフェン系ナノ複合材料の合成のために、有毒性添加物の使用、多段階の複雑な工程、数時間から数日にわたる長い合成時間や多くのエネルギーを消費する工程を適用している。   In order to utilize the excellent physical properties of graphene among the nanocomposites, the uniform distribution between graphene and the active material is most important. For this reason, the heterogeneous nucleation of the active material on the surface of the graphene (heterogeneous) Nucleation) has emerged as the most reliable method, and many studies have been conducted to achieve this. Existing studies have shown that for the synthesis of graphene-based nanocomposites with a uniform distribution, the use of toxic additives, multi-step complex processes, long synthesis times ranging from hours to days and many A process that consumes energy is applied.

しかしながら、これでは材料独自の優れた特性にもかかわらず、高い工程コストや環境的負担のため商用化され難いという短所がある。したがって、優れた特性を示すグラフェン系ナノ複合材料を環境にやさしく且つ低い工程コストで合成することができる技術の開発が求められている。   However, this has the disadvantage that it is difficult to commercialize due to high process costs and environmental burdens despite the excellent properties unique to the material. Therefore, development of a technology capable of synthesizing a graphene-based nanocomposite material exhibiting excellent characteristics that is environmentally friendly and at low process costs is required.

そこで、本発明は、従来の多くのエネルギー消費を伴い且つ手間がかかるグラフェン系ナノ複合材料の合成方法の短所を解決して、金属リン酸塩を含む多様な種類の金属酸化物とグラフェンがナノ複合化されたグラフェン系ナノ複合材料を、合成のためのさらなるエネルギーの投入を行うことなく常温で短時間で実現することができる方法及び装置を提供することを目的とする。   Accordingly, the present invention solves the disadvantages of the conventional method of synthesizing graphene-based nanocomposites that require a lot of energy consumption and is troublesome. It is an object of the present invention to provide a method and an apparatus capable of realizing a composite graphene-based nanocomposite material at room temperature in a short time without further energy input for synthesis.

また、本発明は、簡易且つ短時間で金属酸化物とグラフェン材料からナノ複合材料を形成することができる方法及び装置を提供することを他の目的とする。   Another object of the present invention is to provide a method and an apparatus capable of forming a nanocomposite material from a metal oxide and a graphene material in a simple and short time.

前記目的を達成するための本発明は、グラフェンと該グラフェンの一方の面に形成された金属酸化物を含むグラフェン系ナノ複合材料の製造方法であって、
酸化グラフェンが分散された溶液を提供する工程と、
前記酸化グラフェンが分散された溶液に金属酸化物形成用原料物質を添加する工程、及び
前記酸化グラフェンと前記金属酸化物形成用原料物質との酸化還元反応を用いて還元されたグラフェン表面の少なくとも一方の面に前記金属酸化物が形成されたナノ複合材料を形成する工程と、を含み、
前記金属酸化物形成用原料物質の還元電位は１．０Ｖ以下であることを特徴とする。 The present invention for achieving the above object is a method for producing a graphene-based nanocomposite material including graphene and a metal oxide formed on one surface of the graphene,
Providing a solution in which graphene oxide is dispersed;
A step of adding a metal oxide forming raw material to the solution in which the graphene oxide is dispersed, and at least one of graphene surfaces reduced using a redox reaction between the graphene oxide and the metal oxide forming raw material Forming a nanocomposite material having the metal oxide formed on the surface thereof,
The reduction potential of the metal oxide forming raw material is 1.0 V or less.

また、前記金属酸化物形成用原料物質の還元電位は０．８Ｖ以下であることが好ましい。   The reduction potential of the metal oxide forming raw material is preferably 0.8 V or less.

また、前記金属酸化物は、金属リン酸塩、酸化鉄、または酸化スズであってよい。   The metal oxide may be a metal phosphate, iron oxide, or tin oxide.

この場合、前記金属酸化物は、ＦｅＰＯ4、Ｆｅ3Ｏ4、及びＳｎＯ2から選ばれた少なくとも１種であってよい。 In this case, the metal oxide may be at least one selected from FePO 4 , Fe 3 O 4 , and SnO 2 .

また、前記グラフェン系ナノ複合材料は、１０μｍ以下の直径を有することが好ましい。   The graphene nanocomposite material preferably has a diameter of 10 μm or less.

また、本発明は、グラフェン系ナノ複合材料であって、
酸化グラフェンが分散された溶液を提供する工程と、
前記酸化グラフェンが分散された溶液に金属酸化物形成用原料物質を添加する工程、及び
前記酸化グラフェンと前記金属酸化物形成用原料物質との酸化還元反応を用いて還元されたグラフェン表面の少なくとも一方の面に前記金属酸化物が形成されたナノ複合材料を形成する工程と、を実施して調製され、前記金属酸化物形成用原料物質の還元電位は１．０Ｖ以下であることを特徴とする。 Further, the present invention is a graphene-based nanocomposite material,
Providing a solution in which graphene oxide is dispersed;
A step of adding a metal oxide forming raw material to the solution in which the graphene oxide is dispersed, and at least one of graphene surfaces reduced using a redox reaction between the graphene oxide and the metal oxide forming raw material Forming a nanocomposite material in which the metal oxide is formed on the surface thereof, and the reduction potential of the metal oxide-forming raw material is 1.0 V or less .

また、前記金属酸化物形成用原料物質の還元電位は０．８Ｖ以下であることが好ましい。   The reduction potential of the metal oxide forming raw material is preferably 0.8 V or less.

また、前記金属酸化物は、金属リン酸塩、酸化鉄、または酸化スズであってよい。   The metal oxide may be a metal phosphate, iron oxide, or tin oxide.

この場合、前記金属酸化物は、ＦｅＰＯ4、Ｆｅ3Ｏ4、及びＳｎＯ2から選ばれる少なくとも１種であってよい。 In this case, the metal oxide may be at least one selected from FePO 4 , Fe 3 O 4 , and SnO 2 .

本発明に係るナノ複合材料の製造方法によれば、簡易な方法で短時間で金属酸化物／グラフェンナノ複合材料を調製することができる。   According to the method for producing a nanocomposite material of the present invention, a metal oxide / graphene nanocomposite material can be prepared in a short time by a simple method.

本発明の好適な実施例に従ってグラフェン系ナノ複合材料を調製する工程を概略的に示す図である。FIG. 4 schematically illustrates a process for preparing a graphene-based nanocomposite material according to a preferred embodiment of the present invention. 本発明の好適な実施例に従って調製されたＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＴＥＭ写真である。 2 is a TEM photograph of FePO 4 .nH 2 O / graphene nanocomposite prepared according to a preferred embodiment of the present invention. 本発明の好適な実施例に従って調製されたＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＸＡＮＥＳを示す図である。FIG. 6 shows XANES of FePO 4 .nH 2 O / graphene nanocomposite prepared according to a preferred embodiment of the present invention. 酸化グラフェンとＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＸＰＳデータを示す図である。Is a diagram showing XPS data graphene oxide and FePO 4 · nH 2 O / graphene composite. 酸化グラフェンとＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＸＰＳデータを示す図である。Is a diagram showing XPS data graphene oxide and FePO 4 · nH 2 O / graphene composite. 酸化グラフェンとＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＦＴ−ＩＲデータを示す図である。It is a diagram showing the FT-IR data of the graphene oxide and FePO 4 · nH 2 O / graphene composite. ＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料の電流密度による容量の変化を示す図である。It is a graph showing changes in capacitance due to the current density of the FePO 4 · nH 2 O / graphene composite. ＦｅＰＯ4・ｎＨ2Ｏの担持量によるＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＸＰＳデータを示す図である。FePO shows the XPS data of the FePO 4 · nH 2 O / graphene composite material according to 4 · nH 2 O loading amount. ＦｅＰＯ4・ｎＨ2Ｏの担持量によるＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＸＰＳデータを示す図である。FePO shows the XPS data of the FePO 4 · nH 2 O / graphene composite material according to 4 · nH 2 O loading amount. ＦｅＰＯ4・ｎＨ2Ｏの担持量によるＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＸＰＳデータを示す図である。FePO shows the XPS data of the FePO 4 · nH 2 O / graphene composite material according to 4 · nH 2 O loading amount. 本発明の好適な実施例に係る酸化還元反応を用いて合成されたＦｅ3Ｏ4／グラフェンナノ複合材料のＸＲＤデータである。 3 is XRD data of an Fe 3 O 4 / graphene nanocomposite synthesized using a redox reaction according to a preferred embodiment of the present invention. 本発明の好適な実施例に係る酸化還元反応を用いて合成されたＦｅ3Ｏ4／グラフェンナノ複合材料のＴＥＭ写真である。 3 is a TEM photograph of an Fe 3 O 4 / graphene nanocomposite synthesized using a redox reaction according to a preferred embodiment of the present invention. 本発明の好適な実施例に係る酸化還元反応を用いて合成されたＦｅ3Ｏ4／グラフェンナノ複合材料のＴＥＭ写真である。 3 is a TEM photograph of an Fe 3 O 4 / graphene nanocomposite synthesized using a redox reaction according to a preferred embodiment of the present invention. 本発明の好適な実施例に係る酸化還元反応を用いて合成されたＳｎＯ2／グラフェンナノ複合材料のＸＲＤデータである。3 is XRD data of a SnO 2 / graphene nanocomposite synthesized using a redox reaction according to a preferred embodiment of the present invention. 本発明の好適な実施例に係る酸化還元反応を用いて合成されたＳｎＯ2／グラフェンナノ複合材料のＴＥＭ写真である。3 is a TEM photograph of a SnO 2 / graphene nanocomposite synthesized using a redox reaction according to a preferred embodiment of the present invention. 本発明の好適な実施例に係る酸化還元反応を用いて合成されたＳｎＯ2／グラフェンナノ複合材料のＴＥＭ写真である。3 is a TEM photograph of a SnO 2 / graphene nanocomposite synthesized using a redox reaction according to a preferred embodiment of the present invention.

以下、本発明の好適な実施例に係るグラフェンと該グラフェンの一方の面に形成された金属酸化物を含むグラフェン系ナノ複合材料及びその製造方法について説明する。   Hereinafter, a graphene-based nanocomposite material including graphene according to a preferred embodiment of the present invention, a metal oxide formed on one surface of the graphene, and a manufacturing method thereof will be described.

図１は、本発明の好適な実施例に従ってグラフェン系ナノ複合材料を調製する工程を概略的に示す図である。   FIG. 1 schematically illustrates a process for preparing a graphene-based nanocomposite material according to a preferred embodiment of the present invention.

図１に示すように、先ず、酸化グラフェン（Ｇｒａｐｈｅｎｅ Ｏｘｉｄｅ）試片を溶媒に分散させてなる酸化グラフェンが分散された溶液を準備する。前記酸化グラフェン試片はグラフェンナノ複合材料を形成したい大きさで提供することが好ましい。また、特にその大きさを限定するものではないが、グラフェン系ナノ複合材料の大きさはグラフェンの大きさによって決められ、グラフェンは通常、数μｍ程度の大きさを有する。   As shown in FIG. 1, first, a solution in which graphene oxide is dispersed by preparing a graphene oxide specimen in a solvent is prepared. The graphene oxide specimen is preferably provided in a size in which a graphene nanocomposite material is desired to be formed. Although the size is not particularly limited, the size of the graphene nanocomposite material is determined by the size of the graphene, and the graphene usually has a size of about several μm.

次いで、前記酸化グラフェンが分散された溶液にグラフェン上に形成したい金属酸化物形成用原料物質を投入する。本発明の好適な実施例では、金属リン酸塩をグラフェン表面に形成するためにリン酸（ＰＯ4 3-）溶液及び鉄イオン（Ｆｅ2+）が含まれた溶液をそれぞれ酸化グラフェンが分散された溶液に投入した。 Next, a raw material material for forming a metal oxide to be formed on the graphene is introduced into the solution in which the graphene oxide is dispersed. In a preferred embodiment of the present invention, graphene oxide is dispersed in a phosphoric acid (PO 4 3− ) solution and a solution containing iron ions (Fe 2+ ), respectively, in order to form a metal phosphate on the graphene surface. Into the solution.

そうすると、酸化グラフェンが分散された溶液中の酸化グラフェンは還元反応を起こして還元されたグラフェン薄膜を形成し、金属イオン（Ｆｅ2+）は酸化反応を起こしてＦｅ3+イオンに酸化されてＦｅＰＯ4・ｎＨ2Ｏを形成し、前記ＦｅＰＯ4・ｎＨ2Ｏは還元されたグラフェンの少なくとも一方の面に蒸着される。すなわち、本発明の好適な実施例に係る方法によれば、別途の加熱やエージング（Ａｇｉｎｇ）工程を行うことなく、金属酸化物／グラフェンナノ複合材料を形成することができる。 Then, the graphene oxide in the solution in which graphene oxide is dispersed causes a reduction reaction to form a reduced graphene thin film, and the metal ion (Fe 2+ ) undergoes an oxidation reaction and is oxidized to Fe 3+ ions to form FePO +. 4 · nH 2 O is formed, and the FePO 4 · nH 2 O is deposited on at least one surface of the reduced graphene. That is, according to the method according to a preferred embodiment of the present invention, a metal oxide / graphene nanocomposite can be formed without performing a separate heating or aging process.

一方、本発明によれば、金属酸化物形成用原料物質と酸化グラフェンとは酸化還元反応を起こす必要があるため、金属酸化物形成用原料物質の還元電位は１．０Ｖ以下である必要があり、なお、円滑且つ迅速な反応のために金属酸化物形成用原料物質の還元電位は０．８Ｖ以下であることがより好ましい。   On the other hand, according to the present invention, since the metal oxide forming raw material and graphene oxide need to undergo a redox reaction, the reduction potential of the metal oxide forming raw material needs to be 1.0 V or less. In addition, it is more preferable that the reduction potential of the metal oxide forming raw material is 0.8 V or less for a smooth and rapid reaction.

また、前記金属酸化物粒子の粒径は小さいほど活用度がアップするため、本発明の好適な実施例に係る金属酸化物粒子は１０ｎｍ以下であることが好ましく、５ｎｍ以下であることがより好ましい。   In addition, since the degree of utilization increases as the particle size of the metal oxide particles is smaller, the metal oxide particles according to a preferred embodiment of the present invention is preferably 10 nm or less, more preferably 5 nm or less. .

図２は、本発明の好適な実施例に従って調製されたＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＴＥＭ写真である。同図中の上図を参考すると、ＦｅＰＯ4・ｎＨ2Ｏナノ粒子がグラフェン表面に均一に分布されたことを確認することができ、本実施例で析出されたＦｅＰＯ4・ｎＨ2Ｏ粒子は約５ｎｍの大きさを有する。また、同図の左下図を参考すると、長範囲にわたってナノ複合材料が均一に合成されたことを確認することができる。また、同図の右下図を参考すると、ナノ複合材料においてＦｅ、Ｐ、Ｏ、Ｃが均一に分布されていることを確認することができる。 FIG. 2 is a TEM photograph of an FePO 4 .nH 2 O / graphene nanocomposite prepared according to a preferred embodiment of the present invention. Referring to the upper figure in the figure, it can be confirmed that the FePO 4 .nH 2 O nanoparticles are uniformly distributed on the graphene surface, and the FePO 4 .nH 2 O particles precipitated in this example are It has a size of about 5 nm. In addition, referring to the lower left diagram of the figure, it can be confirmed that the nanocomposite material was uniformly synthesized over a long range. In addition, referring to the lower right diagram of the figure, it can be confirmed that Fe, P, O, and C are uniformly distributed in the nanocomposite material.

図３は、本発明の好適な実施例に従って調製されたＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＸＡＮＥＳ（Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｎｅａｒ Ｅｄｇｅ Ｓｔｒｕｃｔｕｒｅ）を示す図である。ＸＡＮＥＳは、物質の酸価を確認することができる分析方法であって、物質の酸価に応じてピークの位置が変わるため、定性的に酸価を分析することができる。同図に示すように、ＦｅＰＯ4・ｎＨ2Ｏは、酸価が２＋であるＦｅＳＯ4・７Ｈ2Ｏから合成され、合成されたＦｅＰＯ4・ｎＨ2Ｏは商用のＦｅＰＯ4のような３＋の酸価を示すことを確認することができる。これより、本発明の好適な実施例に係る酸化還元反応によってＦｅイオンが酸化されたことを確認することができる。 FIG. 3 is a diagram illustrating XANES (X-ray Absorption Near Edge Structure) of FePO 4 .nH 2 O / graphene nanocomposite prepared according to a preferred embodiment of the present invention. XANES is an analysis method capable of confirming the acid value of a substance, and the position of the peak changes according to the acid value of the substance, so that the acid value can be analyzed qualitatively. As shown in the figure, FePO 4 · nH 2 O is synthesized from FeSO 4 · 7H 2 O having an acid value of 2+, and the synthesized FePO 4 · nH 2 O is 3+ like commercial FePO 4. It can be confirmed that the acid value is shown. From this, it can be confirmed that Fe ions were oxidized by the oxidation-reduction reaction according to the preferred embodiment of the present invention.

図４（ａ）は、酸化グラフェンのＸＰＳデータを示す図である。図４（ａ）に示すようにグラフェンの酸化のために適用されたハマー法（Ｈｕｍｍｅｒｓ ｍｅｔｈｏｄ）によって表面にＣ−Ｏ、Ｃ＝Ｏ、Ｃ（Ｏ）Ｏなど多数の官能基が存在することを確認することができる。また、図４（ｂ）は、ＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＸＰＳデータを示す図である。図４（ｂ）に示すように酸化グラフェンの還元反応後、Ｃ−Ｏ官能基の数が大きく減少したことを確認することができ、これは、酸化グラフェンと金属酸化物原料物質との酸化還元反応によって酸化グラフェンがグラフェン（ＲＧＯ；Ｒｅｄｕｃｅｄ Ｇｒａｐｈｅｎｅ Ｏｘｉｄｅ）に還元されたことを示す。 FIG. 4A shows XPS data of graphene oxide. As shown in FIG. 4A, the presence of a large number of functional groups such as C—O, C═O, and C (O) O on the surface by the Hummers method applied for graphene oxidation. Can be confirmed. FIG. 4B is a diagram showing XPS data of the FePO 4 · nH 2 O / graphene nanocomposite. As shown in FIG. 4B, after the reduction reaction of graphene oxide, it can be confirmed that the number of CO functional groups is greatly reduced. This is due to the oxidation-reduction between graphene oxide and the metal oxide raw material. It shows that graphene oxide was reduced to graphene (RGO; Reduced Graphene Oxide) by the reaction.

図５は、酸化グラフェンとＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＦＴ−ＩＲ（Ｆｏｕｒｉｅｒ Ｔｒａｎｓｆｏｒｍ ＩｎｆｒａＲｅｄ ｓｐｅｃｔｒｏｓｃｏｐｙ）データを示す図である。酸化グラフェンとＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のデータを比べると、ナノ複合材料の合成後、酸化グラフェンの表面に存在する官能基が除去されたことを確認することができ、これは、酸化還元反応後に酸化グラフェン（ＧＯ）がグラフェン（ＲＧＯ）に還元されたことを示す。 FIG. 5 is a diagram showing FT-IR (Fourier Transform InfraRed spectroscopy) data of graphene oxide and FePO 4 .nH 2 O / graphene nanocomposite. Comparing the data of graphene oxide and FePO 4 · nH 2 O / graphene nanocomposite, we can confirm that the functional groups present on the surface of graphene oxide were removed after the synthesis of the nanocomposite. , Graphene oxide (GO) is reduced to graphene (RGO) after the redox reaction.

図６は、ＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料の電流密度による容量の変化を示す図である。一般に、ナノ複合材料中の活物質の担持量が増加すれば高率放電特性が低下するのに対し、図６に示すように本発明の好適な実施例に係るナノ複合材料では、活物質の担持量が増加しているにもかかわらず、高率放電特性が低下しないことを確認することができる。 FIG. 6 is a diagram showing a change in capacity depending on the current density of the FePO 4 .nH 2 O / graphene nanocomposite. In general, as the amount of active material supported in the nanocomposite increases, the high rate discharge characteristic decreases, whereas in the nanocomposite according to the preferred embodiment of the present invention, as shown in FIG. It can be confirmed that the high-rate discharge characteristics do not deteriorate despite the increase in the loading amount.

図７は、ＦｅＰＯ4・ｎＨ2Ｏの担持量によるＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料のＸＰＳデータを示す図であって、図７（ａ）はＦｅＰＯ4・ｎＨ2Ｏが９１％、図７（ｂ）は８４％、図７（c）は７３％がそれぞれ担持された場合を示す。同図に示すように、活物質の担持量の増加に伴い、Ｃ−Ｏ官能基が減少することを確認することができ、これにより、酸化還元反応で合成されたＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料は、グラフェン（ＲＧＯ）の活物質担持量が高いほど、より優れた電気伝導度を示すことを予測することができる。したがって、ＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料は、グラフェン（ＲＧＯ）の活物質担持量を調節することで電気伝導度を容易に調節することができる。 Figure 7 is a diagram showing XPS data of FePO 4 · nH 2 O / graphene composite material according to the loading amount of FePO 4 · nH 2 O, 7 (a) is FePO 4 · nH 2 O 91% FIG. 7B shows a case where 84% is carried and FIG. 7C shows a case where 73% is carried. As shown in the figure, it can be confirmed that the CO functional group decreases with an increase in the amount of the active material supported. As a result, FePO 4 .nH 2 O / synthesized by the oxidation-reduction reaction can be confirmed. It can be predicted that the graphene nanocomposite material exhibits better electrical conductivity as the amount of graphene (RGO) active material supported is higher. Therefore, the electric conductivity of the FePO 4 .nH 2 O / graphene nanocomposite can be easily adjusted by adjusting the amount of graphene (RGO) active material supported.

図８（ａ）は、本発明の好適な実施例に係る酸化還元反応を用いて合成されたＦｅ3Ｏ4／グラフェンナノ複合材料のＸＲＤデータ、図８（ｂ）及び図８（ｃ）は、本発明の好適な実施例に係る酸化還元反応を用いて合成されたＦｅ3Ｏ4／グラフェンナノ複合材料のＴＥＭ写真である。また、図９（ａ）は、本発明の好適な実施例に係る酸化還元反応を用いて合成されたＳｎＯ2／グラフェンナノ複合材料のＸＲＤデータ、図９（ｂ）及び図９（ｃ）は、本発明の好適な実施例に係る酸化還元反応を用いて合成されたＳｎＯ2／グラフェンナノ複合材料のＴＥＭ写真である。図８及び図９に示すように、先に説明したＦｅＰＯ4・ｎＨ2Ｏ／グラフェンナノ複合材料の他にも、本発明の好適な実施例に係る方法を用いれば、Ｆｅ3Ｏ4／グラフェンナノ複合材料、ＳｎＯ2／グラフェンナノ複合材料など、金属酸化物形成用原料物質の還元電位が１Ｖ以下の他の金属酸化物が合成されたナノ複合材料を容易に得られることを確認することができる。 FIG. 8A is an XRD data of Fe 3 O 4 / graphene nanocomposite synthesized using a redox reaction according to a preferred embodiment of the present invention, FIG. 8B and FIG. 4 is a TEM photograph of an Fe 3 O 4 / graphene nanocomposite synthesized using a redox reaction according to a preferred embodiment of the present invention. FIG. 9A shows XRD data of a SnO 2 / graphene nanocomposite synthesized using a redox reaction according to a preferred embodiment of the present invention. FIG. 9B and FIG. 3 is a TEM photograph of a SnO 2 / graphene nanocomposite synthesized using a redox reaction according to a preferred embodiment of the present invention. As shown in FIGS. 8 and 9, in addition to the FePO 4 .nH 2 O / graphene nanocomposite described above, if the method according to the preferred embodiment of the present invention is used, Fe 3 O 4 / graphene It can be confirmed that nanocomposites such as nanocomposites and SnO 2 / graphene nanocomposites can be easily obtained by synthesizing other metal oxides having a reduction potential of 1 V or less of the raw material for forming metal oxides. it can.

以上、本発明の好適な実施例に係る金属酸化物を含むグラフェン系ナノ複合材料及びその製造方法を詳細に説明した。しかし、本発明の属する技術分野における通常の知識を有する者であれば前記構成に対する種々の修正及び変形が可能であることが理解できるであろう。したがって、本発明の範囲は特許請求の範囲によってのみ限定される。   As described above, the graphene-based nanocomposite material including the metal oxide according to the preferred embodiment of the present invention and the manufacturing method thereof have been described in detail. However, those skilled in the art to which the present invention pertains can understand that various modifications and variations can be made to the above configuration. Accordingly, the scope of the invention is limited only by the claims.

Claims (10)

グラフェンと該グラフェンの一方の面に形成された金属酸化物を含むグラフェン系ナノ複合材料の製造方法であって、
酸化グラフェンが分散された溶液を調製する工程と、
前記酸化グラフェンが分散された溶液に金属酸化物形成用原料物質を添加する工程、及び
前記酸化グラフェンと前記金属酸化物形成用原料物質との酸化還元反応を用いて還元されたグラフェン表面の少なくとも一方の面に前記金属酸化物を形成することによりナノ複合材料を形成する工程と、を含み、
前記金属酸化物形成用原料物質の還元電位は１．０Ｖ以下であることを特徴とするグラフェン系ナノ複合材料の製造方法。 A method for producing a graphene-based nanocomposite material including graphene and a metal oxide formed on one surface of the graphene,
Preparing a solution in which graphene oxide is dispersed;
A step of adding a metal oxide forming raw material to the solution in which the graphene oxide is dispersed, and at least one of graphene surfaces reduced using a redox reaction between the graphene oxide and the metal oxide forming raw material Forming a nanocomposite material by forming the metal oxide on the surface of
The method for producing a graphene-based nanocomposite, wherein the metal oxide-forming raw material has a reduction potential of 1.0 V or less. 前記金属酸化物形成用原料物質の還元電位は、０．８Ｖ以下である請求項１に記載の製造方法。   The manufacturing method according to claim 1, wherein the reduction potential of the metal oxide forming raw material is 0.8 V or less. 前記金属酸化物は、金属リン酸塩、酸化鉄及び酸化スズからなる群から選択された１つを含む請求項２に記載の製造方法。   The manufacturing method according to claim 2, wherein the metal oxide includes one selected from the group consisting of metal phosphate, iron oxide, and tin oxide. 前記金属酸化物は、ＦｅＰＯ4、Ｆｅ3Ｏ4及びＳｎＯ2からなる群から選択された１つを含む請求項３に記載の製造方法。 The manufacturing method according to claim 3, wherein the metal oxide includes one selected from the group consisting of FePO 4 , Fe 3 O 4, and SnO 2 . 前記グラフェン系ナノ複合材料は、１０μｍ以下の直径を有するナノ材料を含む請求項１〜４の何れかに記載の製造方法。   The manufacturing method according to claim 1, wherein the graphene-based nanocomposite material includes a nanomaterial having a diameter of 10 μm or less. グラフェンと該グラフェンの一方の面に形成された金属酸化物を含むグラフェン系ナノ複合材料であって、
酸化グラフェンが分散された溶液を調製する工程と、
前記酸化グラフェンが分散された溶液に金属酸化物形成用原料物質を添加する工程、及び
前記酸化グラフェンと前記金属酸化物形成用原料物質との酸化還元反応を用いて還元されたグラフェン表面の少なくとも一方の面に前記金属酸化物を形成することによりナノ複合材料を形成する工程を含み、
前記金属酸化物形成用原料物質の還元電位は１．０Ｖ以下である方法により調製された、グラフェン系ナノ複合材料。 A graphene-based nanocomposite material including graphene and a metal oxide formed on one surface of the graphene,
Preparing a solution in which graphene oxide is dispersed;
A step of adding a metal oxide forming raw material to the solution in which the graphene oxide is dispersed, and at least one of graphene surfaces reduced using a redox reaction between the graphene oxide and the metal oxide forming raw material Forming a nanocomposite by forming the metal oxide on the surface of
A graphene-based nanocomposite material prepared by a method in which the metal oxide-forming raw material has a reduction potential of 1.0 V or less. 前記金属酸化物形成用原料物質の還元電位は、０．８Ｖ以下である請求項６に記載のグラフェン系ナノ複合材料。   The graphene-based nanocomposite material according to claim 6, wherein the reduction potential of the metal oxide forming raw material is 0.8 V or less. 前記金属酸化物は、金属リン酸塩、酸化鉄及び酸化スズからなる群から選択される１つを含む請求項７に記載のグラフェン系ナノ複合材料。   The graphene-based nanocomposite material according to claim 7, wherein the metal oxide includes one selected from the group consisting of metal phosphate, iron oxide, and tin oxide. 前記金属酸化物は、ＦｅＰＯ4、Ｆｅ3Ｏ4及びＳｎＯ2からなる群から選択された１つを含む請求項８に記載のグラフェン系ナノ複合材料。 The graphene-based nanocomposite material according to claim 8, wherein the metal oxide includes one selected from the group consisting of FePO 4 , Fe 3 O 4, and SnO 2 . 前記グラフェン系ナノ複合材料は、１０μｍ以下の直径を有するナノ材料を含む請求項６〜９の何れかに記載のグラフェン系ナノ複合材料。   The graphene-based nanocomposite material according to claim 6, wherein the graphene-based nanocomposite material includes a nanomaterial having a diameter of 10 μm or less.
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KR101945818B1 (en) 2011-10-04 2019-02-08 성균관대학교산학협력단 Composite containing metal component supported on graphene, preparing method of the same, and uses of the same

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