수열합성 조건에 따른 나노로드 클러스터형 MnO2의 상변화와 이를 이용한 LiMn2O4의 리튬이온전지 양전극 특성

강근영; 최민규; 이영기; 김광만; Kun-Young Kang; Min Gyu Choi; Young-Gi Lee; Kwang Man Kim

Korean Chemical Engineering Research, Vol.49, No.5, 541-547, October, 2011

Phase Change of Nanorod-Clustered MnO2 by Hydrothermal Reaction Conditions and the Lithium-ion Battery Cathode Properties of LiMn2O4 Prepared from the MnO2

강근영, 최민규, 이영기, 김광만^†

한국전자통신연구원 융합부품소재부문 전력제어소자팀, 305-700 대전광역시 유성구 가정로 218

Kun-Young Kang, Min Gyu Choi, Young-Gi Lee, and Kwang Man Kim^†

Research Team of Power Control Devices, Electronics and Telecommunications Research Institute(ETRI), 218 Gajung-ro, Yuseong-gu, Daejon 305-700, Korea

E-mail:

초록

MnSO45H2O와 (NH4)S2O8의 수열반응으로 1차원 나노로드들이 침상으로 클러스터화된 구조의 MnO2를 제조하고 그 모폴로지와 결정성을 분석하였다. 수열반응의 조건에 따라 α-, β-, γ-MnO2 등의 전구체가 제조될 수 있는데, 고농도 반응물 및 높은 수열합성 온도(150 ℃)에서 전기화학적 활성이 우수한 나노로드 클러스터 β-MnO2의 생성을 확인하였다. 또한 리튬화제 LiC3H3O22·H2O의 농도와 열처리 온도를 변화시키면서 MnO2를 리튬화하여 스피넬계 LiMn2O4를 제조하고 리튬이온전지 양전극으로서의 특성을 조사하였다. 결과적으로 나노로드 클러스터형 β-MnO2로부터 고농도 리튬화제와 800 ℃ 열처리를 통해 제조한 LiMn2O4가 정방형 스피넬에 가장 가까운 구조임을 확인하였으며, 120mAh/g의 우수한 초기 방전용량을 나타내었다.

Nanorod-clustered MnO2 precursors with α-, β-, and γ-phases are synthesized by hydrothermal reaction of MnSO45H2O and (NH4)S2O8. The formation of nanorod-clustered β-MnO2 is particularly confirmed under the conditions of high reactant concentration and hydrothermal reaction at 150℃. The spinel LiMn2O4 nanorod-clusters are also prepared by lithiating the MnO2 precursors, varying the concentration of lithiating agent (LiC3H3O2·2H2O) and heat treatment temperature, and characterized for use as cathode material of lithium-ion batteries. As a result, the nanorodclustered LiMn2O4 prepared from the β-MnO2 at higher LiC3H3O2·2H2O concentration and the annealing at 800 ℃ is proven to show the cubic spinel structure and to achieve the high initial discharge capacity of 120 mAh/g.

Keywords:MnO2;Hydrothermal Synthesis;LiMn2O4;Lithium-ion Battery;Cathode

[References]

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Tang W, Yang X, Liu Z, Ooi K, J. Mater. Chem., 13, 2989 (2003)
Luo JY, Zhang JJ, Xia YY, Chem. Mater., 18, 5618 (2006)
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Huang XK, Lv DP, Zhang QS, Chang HT, Gan JL, Yang Y, Electrochim. Acta, 55(17), 4915 (2010)

[Referenced By]

[1] Curtis CJ, Wang J, Schulz DL, J. Electrochem. Soc., 151, ㅁ590 (2004)

[2] Li NC, Patrissi CJ, Che GL, Martin CR, J. Electrochem. Soc., 147(6), 2044 (2000)

[3] Li XX, Cheng FY, Guo B, Chen J, J. Phys. Chem. B, 109(29), 14017 (2005)

[4] Luo JY, Cheng L, Xia YY, Electrochem. Commun., 9, 1404 (2007)

[5] Luo JY, Xiong HM, Xia YY, J. Phys. Chem. C., 112, 12051 (2008)

[6] Cao AM, Hu JS, Liang HP, Wan LJ, Angew. Chem. Intern. Ed., 44, 4391 (2005)

[7] Wang X, Li Y, Chem. Commun., 764 (2002)

[8] Wang X, Li YD, J. Am. Chem. Soc., 124(12), 2880 (2002)

[9] Yuan JK, Li WN, Gomez S, Suib SL, J. Am. Chem. Soc., 127(41), 14184 (2005)

[10] Thackeray MM, Prog. Solid State Chem., 25, 1 (1997)

[11] Bao SJ, Li CM, Li HL, Luong JHT, J. Power Sources, 164(2), 885 (2007)

[12] Jiang CH, Dou SX, Liu HK, Ichihara M, Zhou HS, J. Power Sources, 172(1), 410 (2007)

[13] Fang HS, Li LP, Yang Y, Yan GF, Li GS, J. Power Sources, 184(2), 494 (2008)

[14] Shaju KM, Bruce PG, Chem. Mater., 20, 5557 (2008)

[15] Kim DK, Muralidharan P, Lee HW, Ruffo R, Yang Y, Chan CK, Peng H, Huggins RA, Cui Y, Nano Lett., 8, 3948 (2008)

[16] Hosono E, Kudo T, Honma I, Matsuda H, Zhou H, Nano Lett., 9, 1045 (2009)

[17] Cho J, J. Mater. Chem., 18, 2257 (2008)

[18] Tang W, Yang X, Liu Z, Ooi K, J. Mater. Chem., 13, 2989 (2003)

[19] Luo JY, Zhang JJ, Xia YY, Chem. Mater., 18, 5618 (2006)

[20] Jiao F, Bruce PG, Adv. Mater., 19, 65 (2007)

[21] Kim IY, Ha HW, Kim TW, Paik Y, Choy JH, Hwang SJ, J. Phys. Chem. C., 113, 21274 (2009)

[22] Huang XK, Lv DP, Zhang QS, Chang HT, Gan JL, Yang Y, Electrochim. Acta, 55(17), 4915 (2010)