中文摘要
本研究之目的在於開發具有高充放速率能力和高循環壽命之先
進式鋰離子電池層狀陰極材料。為了完成這個目標，我們採用新穎合
成方式製造高密度球狀粒子，更進一步將以金屬氧化物修飾其表面，
來獲得高可逆電容量、高充放速率能力、高循環壽命的陰極材料。
由於LiNi1/3Co1/3Mn1/3O2具有高電壓及高可逆電容量，其被視為最
具潛力的鋰離子二次電池的陰極材料，我們結合共沈澱法與噴霧乾燥
法合成球狀LiNi1/3Co1/3Mn1/3O2，並藉由ZrO2、TiO2、 Al2O3和AlPO4修
飾合成LiNi1/3Co1/3Mn1/3O2的表面。為了鑑定材料的特性，應用了粉末
繞射儀、感應耦合電漿原子放射光譜儀、掃瞄式電子顯微鏡、穿透式
電子顯微鏡，獲得修飾前後的LiNi1/3Co1/3Mn1/3O2的相圖、元素劑量、
粒子尺寸、表面型態、及表面修飾化合物的物性。此外以熱示差掃瞄
卡計及化學分析電子儀評估其熱穩定性及過渡金屬的氧化價數。
由粉末繞射圖譜顯示，藉由ZrO2、TiO2、Al2O3和AlPO4修飾前後
的LiNi1/3Co1/3Mn1/3O2均為層狀材料，掃瞄式電子顯微鏡微影像顯示，
修飾前後的陰極材料有部分奈米孔洞，而穿透式電子顯微鏡的影像發
現修飾層均勻分佈在陰極材料表面，再由化學分析電子儀判定鎳、
鈷、錳的氧化價數為二價、三價、四價。
為了評估修飾前後的LiNi1/3Co1/3Mn1/3O2之充放電速率能力，於室
溫下在3.0 ~ 4.5 V的範圍內，以不同的充放電速率(0.1 ~ 1.0 C) 將修飾
前後的LiNi1/3Co1/3Mn1/3O2 做測試， 相較所有修飾前後的
LiNi1/3Co1/3Mn1/3O2，其中LiNi1/3Co1/3Mn1/3O2@ZrO2有最佳的可逆電容
量、最高的放電電壓平台、最優秀的充放電速率能力與循環壽命的電
化學表現，經由極化測試分析獲得證據，得知改善表面性質後，
LiNi1/3Co1/3Mn1/3O2@ZrO2其極化情形最少，因此可獲得較佳之電化學
特性。我們將不同表面修飾材料的極片，充電至4.5 V之電壓後，作
熱穩定分析，由熱示差掃瞄卡計的分析，發現不同金屬氧化物修飾後
的極片，相較於未修飾材料的極片和商業化的LiCoO2，極片釋放較低
的能量，顯示修飾後材料的極片所組成的電池，有較高的安全性。
根據實驗結果，顯示合成之LiNi1/3Co1/3Mn1/3O2@ZrO2材料，展現
最佳的可逆電容量、充放電速率能力及循環壽命的電化學特性。具有
可當作新一代能量來源的的鋰電子電池之潛力。

ABSTRACT

The purpose of this study is to develop high rate capability and high
cyclability of layered cathode material for an advanced lithium-ion
batteries (LiBs). In order to achieve the goal, we have employed a novel
synthesis process that can produce high density spherical particles and
their surface was modified further by coating with appropriate metal
oxides to obtain the cathode materials with high reversible capacity, high
rate capability and better cycleability.
The LiNi1/3Co1/3Mn1/3O2 electrode is the most promising cathode for
rechargeable lithium batteries owing to its high reversible capacity at
higher potential. We have prepared LiNi1/3Co1/3Mn1/3O2 material by
co-precipitation and spray drying process and the resulted electrode
powder was modified by coating with ZrO2, TiO2, Al2O3 and AlPO4 on its
surface. The phase purity, elemental analysis, particles size and surface
morphology and the nature of coating on the electrode surface of the bare
and modified electrodes were determined, respectively, by employing the
X-ray diffraction (XRD), inductively coupled plasma - Atomic emission
spectrometer (ICP-AES), Scanning electron microscopy (SEM) and
Transmission Electron Microscopy (TEM) techniques. Further, we have
evaluated the thermal stability of the bare and the modified electrodes by
means of Differential Scanning Calorimetry (DSC) and also the existence
of chemical states of transition metals (Ni, Co and Mn) were determined
by Electron Spectroscopy for Chemical Analysis (ESCA).
The XRD pattern analysis revealed that the LiNi1/3Co1/3Mn1/3O2 of both
bare and modified by coating with ZrO2, TiO2, Al2O3 and AlPO4 electrode
materials were found to be single phase and layer structure. The SEM
micrographs of the bare and the modified electrode powder showed
partial nanopore and the coating layer on the surface of the modified
electrode was found to be uniform as evidenced from TEM micrographs.
The chemical states of Ni, Co and Mn were determined as Ni2+, Co3+ and
Mn4+ from the ESCA analysis.
The electrochemical cycle performance of the LiNi1/3Co1/3Mn1/3O2
electrode was determined at various C-rates (0.1 ~ 1.0 C) in the potentials
at 3.0 ~ 4.5 V at ambient temperature in order to evaluate the rate
capability of the bare and the modified electrode materials. The

LiNi1/3Co1/3Mn1/3O2 electrode modified by coating with ZrO2 was capable
of delivering the best electrochemical characteristics of reversible
capacity, rate capability and cyclability among the studied bare and
modified electrodes. The improved electrochemical characteristics of the
modified electrode by coating with ZrO2 may improve the surface
properties of the modified electrode thereby smaller polarization as
evidenced from polarization analysis. we have also determined the
thermal stability of the various electrodes at the end of charged state (4.5
V) and the DSC analysis showed that the electrode modified by coating
with various metal oxides released lower heat compared to that of the
pristine as well as commercial LiCoO2 cathode which indicates that the
higher safety of the battery that can be operated at higher potentials.
Based on various experimental results, we have concluded that the
LiNi1/3Co1/3Mn1/3O2 electrode modified its surface by coating with ZrO2
was found to exhibit the best electrochemical characteristics of reversible
capacity, rate capability and cyclability. The improved electrochemical
properties suggest that the modified electrode can be used as a potential
cathode in the lithium-ion batteries for the next generation power source.
Keywords: Li-ion battery; LiNi1/3Co1/3Mn1/3O2;coating;spherical
致謝

參考文獻
[1]楊模華, 嵌入式過渡金屬氧化物在鋰電池電極材料上的應用. 工
業材料 2000, 157, 144.
[2]Yamaki, J., Tobishima, S., Hayashi, K., Saito, K., Nemoto, Y. and
Arakawa, M. A consideration of the morphology of
electrochemically deposited lithium in an organic electrolyte. J.
Power Sources 1998, 74, (2), 219-227.
[3]Delmas, C., Braconnier, J. J. and Haginmuller, P. A new variety of
LiCoO2 with an unusual oxygen packing obtained by exchange
reaction. Mater. Res. Bull. 1982, 17, 117.
[4]Molenda, J., Stoklosa, A. and Bak, T. Modification in the electronic
structure of cobalt bronze LixCoO2 and the resulting
electrochemical properties. Solid State Ionics 1989, 36, 53.
[5]Passerini, S., Scrosati, B. and Gorenstein, A. The intercalation of
lithium in nickel oxide and its electrochemical properties. J.
Electrochem. Soc. 1990, 137, 3297.
[6]Dahn, J. R., Sacken, U. V. and Michal, C. A. Structure and
electrochemistry of Li1+xNiO2 and A new Li2NiO2 phase with the
Ni(OH)2 structure. Solid State Ionics 1990, 44, 87.
[7]Barker, J., Pynenburg, R. and Koksbang, R. Determination of
thermodynamic, kinetic and interfacial properties for the
Li/LixMn2O4 system by electrochemical technique. J. power
Sources 1994, 52, 185.
[8]Mizushima, K., Jones, P. C., Wiseman, P. J. and Goodenough, J. B.
LixCoO2 (0<x≦1): a new cathode material for batteries of high
energy density. Mat. Res. Bull. 1980, 15, 783.
[9]Gummow, R. J., Thackeray, M. M., Davdid, E. I. F. and Hull, S.
Structure and electrochemistry of lithium cobalt oxide synthesized
at 400 ℃. Mat. Res. Bull. 1992, 27, (327).
[10]Rossen, E., Reimers, J. N. and Dahn, J. R. Synthesis and
electrochemistry of Spinel LT-LiCoO2. Solid State Ionics 1993, 62,
(53).
[11]Dyer, L. D., Borie, B. S. and Smith, G. P. Alkali metal-nickel oxides
123
of the type MNiO2. J. Am. Chem. Soc. 1954, 78, 1499.
[12]Goodenough, J. B., Wickham, D. G. and Croft, W. J. Some
ferromagnetic properties of the system LixNi1-xO2. J. Appl. Phys.
1958, 29, 380.
[13]Ohzuku, T., Ueda, A. and Nagayama, M. Electrochemistry and
structural chemistry of LiNiO2 (R3m) for 4 Volt secondary lithium
cells. J. Electrochem. Soc. 1993, 140, 1862.
[14]Thackeray, M. M., Johnson, P. J., Picciotto, L. A. D., Bruce, P. G.
and Goodenough, J. B. Electrochemical extraction of lithium
from LiMn2O4. Mat. Res. Bull. 1984, 19, 179.
[15]Thackeray, M. M., David, E. I. F., Bruce, P. G. and Goodenough, J.
B. Lithium insertion into manganese spinels. Mat. Res. Bull. 1983,
18, 461.
[16]Todorov, Y., M. Hideshima, Y. Noguchi, H. and Yoshio, M.
Determination of theoretical capacity of metal ion-doped
LiMn2O4 as the positive electrode in Li-ion batteries. J. Power
Sources 1999, 77, 198.
[17]Gummow, R. J., Kock, A. d. and Thackerat, M. M. Improved
capacity retention in rechargeable 4 V lithium/lithium-manganese
oxide (spinel) cells. Solid State Ionics 1994, 69, 59.
[18]Ohzuku, T. and Makimura, Y. Layered Lithium Insertion Material of
LiCo1/3Ni1/3Mn1/3O2 for Lithium-Ion Batteries. Chem. Lett. 2001,
642.
[19]Hwang, B. J., Tsai, Y. W., Carlier, D. and Ceder, G. A combined
computational/experimental study on LiNi1/3Co1/3Mn1/3O2.
Chem. Mater. 2003, 15, (19), 3676-3682.
[20] Lee, M. H., Kang, Y. J., Myung, S. T.and Sun, Y. K. Synthetic
optimization of Li[Ni1/3Co1/3Mn1/3]O2 via co-precipitation.
Electrochim. Acta. 50 (2004) 939–948
[21] Park, S. H., Yoon, C. S., Kang, S. G., Kim, H. S., Moon, S. I. and
Sun, Y. K. Synthesis and structural characterization of layered
Li[Ni1/3Co1/3Mn1/3]O2 cathode materials by ultrasonic spray
pyrolysis method. Electrochim. Acta. 49 (2004) 557–563
[22] Belharouak, I., Sun, Y. K., Liu, J. and Amine,
K.Li(Ni1/3Co1/3Mn1/3)O2 as a suitable cathode forhigh power
applications. J. Power Sources 123 (2003) 247–252
[23] Ying, J., Jiang, C. and Wan, C. Preparation and characterization of
high-density spherical LiCoO2 cathode material for lithium ion
batteries. J. Power Sources 129 (2004) 264–269
[24] Zhou, Y. and Hulin, Li. Sol Gel Template Synthesis of Highly
Ordered LiCo0.5Mn0.5O2 Nanowire Arrays and Their Structural
Properties. J. Solid State chem. 165, 247–253 (2002)
[25] Wang, Y., Takahashi, K., Shang, H. and Cao, G. Synthesis and
Electrochemical Properties of Vanadium Pentoxide Nanotube
Arrays. J. Phys. Chem. B 2005, 109, 3085-3088
[26] Chena, Z. and Dahn, J. R. Effect of a ZrO2 Coating on the Structure
and Electrochemistry of LixCoO2 When Cycled to 4.5 V
Electrochemical and Solid-state Letters, 5 (10) A213-A216 (2002)
[27] Cho, J., Kim, Y. J. and Parkb, B. LiCoO2 Cathode Material That
Does Not Show a Phase Transition from Hexagonal to Monoclinic
Phase. J. Electrochem. Soc, 148 (10) A1110-A1115 (2001)
[28] Luo, P. and Nieh, T.G. Preparing hydroxyapatite powders with
controlled morphology. Biomaterials 17(1996)1959-1964
[29]王志仁，高電容量鋰離子電池層狀陰極材料之研究.國立台灣科
技大學/化學工程系碩士論文 2004.