[논문]Zn 도핑 된 δ-MnO2의 수열반응을 통한 chalcophanite 및 todorokite 결정 생성 및 성장

정해성

doi:10.9713/kcer.2023.61.1.162

Zn 도핑 된 δ-MnO2의 수열반응을 통한 chalcophanite 및 todorokite 결정 생성 및 성장
Formation of Chalcophanite and Todorokite from the Hydrothermal Reaction of Zn-doped δ-MnO2 원문보기

Korean chemical engineering research = 화학공학, v.61 no.1, 2023년, pp.162 - 167

정해성 (창원대학교, 화공시스템공학과)

초록
AI-Helper

망간산화물은 다양한 결정구조를 가지고 있으며, 특히 초기에 생성되는 나노층상구조의 δ-MnO₂ 가 다양한 산화환원 반응에 따라 여러가지 터널 및 층상구조로 변화한다. 최근Zn기반 이차전지에 대한 관심이 증가하고 있지만, 충방전 간 Zn이온이 양극재로 사용되는 망간산화물 결정 구조 변화 및 새로운 결정 생성 등에 미치는 영향에 대한 기초적 이해를 위해 Zn이온이 망간산화물 결정에 미치는 영향에 대한 연구가 더욱 필요하다. 본 연구에서는 수열반응 간 Zn 도핑정도가 조절된 나노층상구조의 δ-MnO₂의 변화를 통해 todorokite과 chalcophanite이 생성 및 성장되는 것을 확인하였고, 반응 시간에 따른 변화과정을 확인하였다. Zn의 양이 많을수록 chalcophanite 결정이 우세하게 생성되었고, 결정 생성이 상대적으로 느린 속도로 발생하는 것을 확인하였다.

Abstract ▼ AI-Helper

Diverse structures of Mn oxides in natural and engineered systems occur from the transformation of δ-MnO2, the most common crystalline phase of nucleated Mn oxides, to other structures via redox reactions, adsorption of metals, etc. Recently, together with emerging interests of Zn-based rechargeable battery systems, which use Mn oxides as a cathode, the transformation and recrystallization of Mn oxides have garnered interests. Here, using hydrothermal reaction of Zn-doped δ-MnO2, the formation of todorokite and chalcophanite is observed. When the concentration of doped Zn increases, the formation of chalcophanite is dominant, but occurs slower than that of the lower concentration of doped Zn. This study will provide a new understanding of the effect of Zn on the recrystallization process of Mn oxides during redox cycles in energy storage systems and environmental systems.

주제어

표/그림 (6)

그림 Fig. 1. Comparison of XRD spectra for hydrothermally reacted δ-MnO₂, Zn5, Zn10, and Zn20 at (A) 0, (B) 2, (C) 8, and (D) 24 hrs. The region of hk band coming from disordered structure of δ-MnO₂ is marked in the box at ~36°. The observed hk band from the all XRD spectra of δ-MnO₂, Zn5, Zn10, and Zn20 in Fig. 1A indicates the disordered layered structure of Mn oxide nanosheets.
$Fig. 2. The formation of chalcophanite and todorokite under hydrothermal reaction of δ-MnO<sub>2</sub>, Zn5, Zn10, and Zn20. (A) Matching diffractions of hydrothermally reacted Mn oxides during 24 hrs with reference of chalcophanite. (B) The structure of chalcophanite. (B) The structure of todorokite.$ 그림 Fig. 2. The formation of chalcophanite and todorokite under hydrothermal reaction of δ-MnO₂, Zn5, Zn10, and Zn20. (A) Matching diffractions of hydrothermally reacted Mn oxides during 24 hrs with reference of chalcophanite. (B) The structure of chalcophanite. (B) The structure of todorokite.
표 Table 1. The sample labels and ratios of Zn/Mn for the synthesized Zn-doped Mn oxides
그림 Fig. 3. Dynamic variation of the crystalline structure of the hydroth time-lapsed conditions.
$Fig. 4. Crystalline sizes of (A) chalcophanite and (B) todorokite transformed from δ-MnO<sub>2</sub>, Zn5, Zn10, Zn20 via the hydrothermal reaction. Using Scherrer Equation, full width half maximum values obtained from the observed diffractions at 9.3° and 18.6°, and at 12.7° and 25.6° provided the crystalline size of todorokite and chalcophanite, respectively.$ 그림 Fig. 4. Crystalline sizes of (A) chalcophanite and (B) todorokite transformed from δ-MnO₂, Zn5, Zn10, Zn20 via the hydrothermal reaction. Using Scherrer Equation, full width half maximum values obtained from the observed diffractions at 9.3° and 18.6°, and at 12.7° and 25.6° provided the crystalline size of todorokite and chalcophanite, respectively.
그림 Fig. 5. FT-IR spectra of the hydrothermally reacted (A) δ-MnO₂, (B) Zn5, (C) Zn10, and (D) Zn20 under varied time conditions.

참고문헌 (18)

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상세보기
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상세보기
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