鋰離子電池高容量富鋰鎳錳氧正極粉體之製備與分析

Synthesis and Characterization of High-capacity Li-rich Nickel Manganese Oxide Cathode for Lithium-ion Batteries

10.6342/NTU.2014.02999

陳文勤

鋰離子電池 ； 富鋰層狀氧化物 ； 形貌變化 ； 石墨烯 ； 導電高分子 ； Li-ion battery ； Li-rich layered oxide ； morphology evolution ； grapheme ； conductive polymer

國立臺灣大學化學工程學系學位論文

2014年

博士

吳乃立

英文

鋰離子電池材料的研發需朝向降低成本與增加電極能量密度兩大方向進行，目前所開發的正極材料中，層狀富鋰鎳錳氧化物，xLi2MnO3•(1 - x)Li(Mn,M)O2,具有>250 mAh/g 的電容量及平均將近4V的氧化還原平台電壓，因此具~1000 WH/kg 的理論比能量潛力，較LiMn2O4、LiNi0.33Co0.33Mn0.33O2 及LiFePO4系統高出甚多。在本論文中，首次利用穿透式X射線顯微術探討層狀富鋰鎳錳氧化物在高溫合成過程中的微結構變化，然而，加熱層狀富鋰鎳錳氧化物的中間過程所產生的輻射狀分布的孔隙結構、少量的孔隙曲折以及較小的晶粒大小具有較小的電子轉移阻抗與增加的鋰離子固態擴散能力而有助於高速充放電的性能。 此外，結果顯示層狀富鋰鎳錳氧化物顆粒表面的過度金屬組成對於微結構與電化學性能有極大的影響。不論是富含錳或鎳的顆粒表面均會造成電容量的損失，而富含鎳的顆粒表面則因較高的電子轉移阻抗及鎳、鋰離子錯位導致其具有較低的電容量與較差的高速充放電能力，不過在循環充放電過程中，富含鎳的表層可以抑制層狀結構轉換成尖晶石的相變化以及伴隨的電壓衰退。此結果提供了一個新的方式，從層狀富鋰鎳錳氧化物顆粒表面過度金屬組成的觀點開發先進的層狀富鋰鎳錳氧化物正極材料。 另一方面，本論文提出兩個方式提升高電極密度(2.5 g/cm3)的鋰離子電池層狀富鋰鎳錳氧化物正極材料的第一圈的庫倫效率、高速充放電的性能以及循環充放電壽命。首先，藉由添加奈米片狀石墨烯在層狀富鋰鎳錳氧電極中，可以減少電極的極化現象且增加比電容量與高速充放電能力，但也促進正極材料與電解液之間鈍化層的生成。此研究是第一次發現石墨烯添加劑造成的負面效應，結果顯示，約100 ppm石墨烯是最適合同時增加高速充放電及循環穩定性的添加劑含量。 另一個改質方法是經由溶液混合且低溫的方式，將導電性高分子聚3,4-二氧乙基噻吩:聚苯乙烯磺酸 (PEDOT:PSS)進行富鋰鎳錳氧化物的表面包覆，經過2 wt.% PEDOT:PSS的包覆後，富鋰鎳錳氧化物的粉體阻抗大量地減少了4個級數，而PEDOT:PSS的包覆含量大於2 wt.%後，粉體阻抗的改善有限。對於電化學測試，顆粒表面的PEDOT:PSS薄膜可以驅使快速的表面電子傳移並提供電極內部高效率的傳導網絡，進而達到快速充放電與電容量的改善與提升；再者，PEDOT:PSS的表面包覆可抑制高電位下SEI的生成，使得富鋰鎳錳氧化物具有較少的第一圈電容量損失以及較高的循環穩定性。

The future development of active materials for lithium ion battery is expected to proceed toward two major directions, namely reducing material cost and increasing electrode energy density. Among the reported cathode materials so far, layered lithium-rich manganese-transition metal oxide composite cathode (abbreviated as LrMOs), xLi2MnO3•(1-x)Li(Mn, M)O2 (M= Mn, Ni, Co), possesses specific capacity of >250mAh/g with an average redox potential near 4V and therefore potential energy density nearly ~1000 WH/kg, which is much higher than those of Li2MnO4, LiNi0.33Co0.33Mn0.33O2 and LiFePO4. In this dissertation, this is the first time that the micro-structural evolution of the resulting LrMOs during calcinations was investigated mainly by transmission X-ray microscopy (TXM). Thus a radially distributed pore pattern, less pore tortuosity and small grain size produced by intermediate heating history, favor the rate performance of the composite oxide cathode due to reduced charge-transfer resistance and enhanced Li ion solid-state diffusivity. Moreover, the microstructures and electrochemical performance are shown to strongly depend on the transition metal composition on the surface of LrMOs particles. the electrodes containing either Mn- or Ni-rich surface cathode lead to capacity loss, while Ni-rich cathode exhibits much lower discharge capacity and poorer rate capability than the one with Mn-rich because of its high charge-transfer resistance and high degree of Ni/Li cations mixing. Nevertheless, the presence of Ni-rich out-layer suppressed the phase transformation from layer to spinel and associated voltage fading during cycling. The results provide a new strategy to develop advanced lithium-rich layered cathode materials from the viewpoints of metal composition on the surface of LrMOs particles. In the other hand, two methods in this dissertation are proposed to enhance the initial coulombic efficiency, rate capability and cycling stability of a highly packed (2.5 g/cm3) LrMOs cathode for lithium ion batteries. First, graphene nanosheets (GNSs) additive into the LrMOs electrodes can reduce electrode polarization and enhance specific capacity and rate performance, and also promote the formation of solid-electrolyte interface (SEI). This study is the first to identify that such an adverse effect is caused by a graphene additive. the results showed that a GNSs additive content of approximately 100 ppm is optimal for achieving both rate and cycle-life enhancements. In the other modification, a conductive polymer, Poly(3,4-ethylene-dioxythiophene):poly(styrene sulfonate) (abbreviated as PEDOT:PSS), was coated on the LrMOs particles by a liquid mixing and low temperature process. It revealed that the resistance of LrMOs powder can be substantially reduced by four orders through 2 wt.% PEDOT:PSS coating, while it have limited improvement of powder resistance when the amount of PEDOT:PSS is above 2 wt.%. For electrochemical test, the presence of PEDOT:PSS film can drive fast electron transport through the surface of the oxide particle and provide efficient conducting network inside the electrode, leading to enhanced rate performance and increased specific capacity for highly packed LrMOs microsphere electrode. Furthermore, the PEDOT:PSS-coated LrMOs exhibited less initial capacity loss and good cycling stability due to inhibited SEI formation under high potentials.

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67. 71. L. Y. Yu, W. H. Qiu, F. Lian, J. Y. Huang, X. L. Kang. "Understanding the phenomenon of increasing capacity of layered 0.65Li[Li1/3Mn2/3]O2･0.35Li(Ni1/3Co1/3Mn1/3)O2", Journal of Alloys and Compounds, 471, 317-321 (2009).
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68. 72. A. R. Armstrong, M. Holzapfel, P. Novak, C. S. Johnson, S. H. Kang, M. M. Thackeray, P. G. Bruce. "Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2", Journal of the American Chemical Society, 128, 8694-8698 (2006).
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69. 73. N. Yabuuchi, K. Yoshii, S. T. Myung, I. Nakai, S. Komaba. "Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li2MnO3-LiCo1/3Ni1/3Mn1/3O2", Journal of the American Chemical Society, 133, 4404-4419 (2011).
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70. 74. C. S. Johnson, J. S. Kim, C. Lefief, N. Li, J. T. Vaughey, M. M. Thackeray. "The significance of the Li2MnO3 component in 'composite' xLi2MnO3･(1-x)LiMn0.5Ni0.5O2 electrodes", Electrochemistry Communications, 6, 1085-1091 (2004).
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71. 75. A. Ito, D. C. Li, Y. Sato, M. Arao, M. Watanabe, M. Hatano, H. Horie, Y. Ohsawa. "Cyclic deterioration and its improvement for Li-rich layered cathode material Li[Ni0.17Li0.2Co0.07Mn0.56]O2", Journal of Power Sources, 195, 567-573 (2010).
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72. 76. S. H. Kang, M. M. Thackeray. "Enhancing the rate capability of high capacity xLi2MnO3･(1-x)LiMO2 (M = Mn, Ni, Co) electrodes by Li-Ni-PO4 treatment", Electrochemistry Communications, 11, 748-751 (2009).
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73. 77. A. D. Robertson, P. G. Bruce. "Mechanism of electrochemical activity in Li2MnO3", Chemistry of Materials, 15, 1984-1992 (2003).
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74. 78. O. Toprakci, H. A. K. Toprakci, Y. Li, L. W. Ji, L. G. Xue, H. Lee, S. Zhang, X. W. Zhang. "Synthesis and characterization of xLi2MnO3･(1-x)LiMn1/3Ni1/3Co1/3O2 composite cathode materials for rechargeable lithium-ion batteries", Journal of Power Sources, 241, 522-528 (2013).
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75. 79. N. Yabuuchi, K. Yamamoto, K. Yoshii, I. Nakai, T. Nishizawa, A. Omaru, T. Toyooka, S. Komaba. "Structural and Electrochemical Characterizations on Li2MnO3-LiCoO2-LiCrO2 System as Positive Electrode Materials for Rechargeable Lithium Batteries", Journal of The Electrochemical Society, 160, A39-A45 (2013).
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76. 80. N. Tran, L. Croguennec, C. Labrugere, C. Jordy, P. Biensan, C. Delmas. "Layered Li1+x(Ni0.425Mn0.425Co0.15)(1-x)O2 positive electrode materials for lithium-ion batteries", Journal of The Electrochemical Society, 153, A261-A269 (2006).
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77. 81. J. Wang, M. H. Zhang, C. L. Tang, Y. G. Xia, Z. P. Liu. "Microwave-irradiation synthesis of Li1.3NixCoyMn1-x-yO2.4 cathode materials for lithium ion batteries", Electrochimica Acta, 80, 15-21 (2012).
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78. 82. L. Li, X. X. Zhang, R. J. Chen, T. L. Zhao, J. Lu, F. Wu, K. Amine. "Synthesis and electrochemical performance of cathode material Li1.2Co0.13Ni0.13Mn0.54O2 from spent lithium-ion batteries", Journal of Power Sources, 249, 28-34 (2014).
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79. 83. X. Jin, Q. J. Xu, X. L. Yuan, L. Z. Zhou, Y. Y. Xia. "Synthesis, characterization and electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode materials for lithium-ion batteries", Electrochimica Acta, 114, 605-610 (2013).
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80. 84. P. G. Bruce, B. Scrosati, J. M. Tarascon. "Nanomaterials for rechargeable lithium batteries", Angewandte Chemie-International Edition, 47, 2930-2946 (2008).
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81. 85. Y. Wang, G. Z. Cao. "Developments in nanostructured cathode materials for high-performance lithium-ion batteries", Advanced Materials, 20, 2251-2269 (2008).
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82. 86. X. Wei, S. C. Zhang, Z. J. Du, P. H. Yang, J. Wang, Y. B. Ren. "Electrochemical performance of high-capacity nanostructured Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for lithium ion battery by hydrothermal method", Electrochimica Acta, 107, 549-554 (2013).
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83. 87. S. X. Liao, Y. J. Zhong, B. H. Zhong, H. Liu, X. D. Guo. "Effective enhancement of electrochemical performance for low-cost cathode material Li1.231Mn0.615Ni0.154O2 via a novel facile hydrothermal modification", Journal of Power Sources, 246, 569-573 (2014).
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84. 88. X. K. Huang, Q. S. Zhang, H. T. Chang, J. L. Gan, H. J. Yue, Y. Yang. "Hydrothermal Synthesis of Nanosized LiMnO2-Li2MnO3 Compounds and Their Electrochemical Performances", Journal of The Electrochemical Society, 156, A162-A168 (2009).
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85. 89. M. G. Kim, M. Jo, Y. S. Hong, J. Cho. "Template-free synthesis of Li[Ni0.25Li0.15Mn0.6]O2 nanowires for high performance lithium battery cathode", Chemical Communications, 218-220 (2009).
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86. 90. M. Gao, F. Lian, H. Q. Liu, C. J. Tian, L. L. Ma, W. Y. Yang. "Synthesis and electrochemical performance of long lifespan Li-rich Li1+x(Ni0.37Mn0.63)(1-x)O2 cathode materials for lithium-ion batteries", Electrochimica Acta, 95, 87-94 (2013).
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87. 91. H. X. Deng, I. Belharouak, R. E. Cook, H. M. Wu, Y. K. Sun, K. Amine. "Nanostructured Lithium Nickel Manganese Oxides for Lithium-Ion Batteries", Journal of The Electrochemical Society, 157, A447-A452 (2010).
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88. 92. D. P. Wang, I. Belharouak, G. M. Koenig, G. W. Zhou, K. Amine. "Growth mechanism of Ni0.3Mn0.7CO3 precursor for high capacity Li-ion battery cathodes", Journal of Materials Chemistry, 21, 9290-9295 (2011).
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89. 93. D. P. Wang, I. Belharouak, S. Gallagher, G. W. Zhou, K. Amine. "Chemistry and electrochemistry of concentric ring cathode Li1.42Ni0.25Mn0.75O2+γ for lithium batteries", Journal of Materials Chemistry, 22, 12039-12045 (2012).
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90. 94. G. Singh, R. Thomas, A. Kumar, R. S. Katiyar, A. Manivannan. "Electrochemical and Structural Investigations on ZnO Treated 0.5Li2MnO3-0.5LiMn0.5Ni0.5O2 Layered Composite Cathode Material for Lithium Ion Battery", Journal of The Electrochemical Society, 159, A470-A478 (2012).
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91. 95. Y. K. Sun, S. T. Myung, B. C. Park, J. Prakash, I. Belharouak, K. Amine. "High-energy cathode material for long-life and safe lithium batteries", Nature Materials, 8, 320-324 (2009).
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92. 96. J. L. Liu, L. Chen, M. Y. Hou, F. Wang, R. C. Che, Y. Y. Xia. "General synthesis of xLi2MnO3･(1-x)LiMn1/3Ni1/3Co1/3O2 nanomaterials by a molten-salt method: towards a high capacity and high power cathode for rechargeable lithium batteries", Journal of Materials Chemistry, 22, 25380-25387 (2012).
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93. 97. Z. Y. Wang, B. A. Li, J. Ma, D. G. Xia. "The Enhanced Electrochemical Performance of Nanocrystalline Li[Li0.26Ni0.11Mn0.63]O2 Synthesized by the Molten-Salt Method for Li-ion batteries", Electrochimica Acta, 117, 285-291 (2014).
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94. 98. J. L. Liu, M. Y. Hou, J. Yi, S. S. Guo, C. X. Wang, Y. Y. Xia. "Improving the electrochemical performance of Layered lithium-rich transition-metal oxides by controlling the structural defects", Energy & Environmental Science, 7, 705-714 (2014).
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95. 99. S. H. Kang, C. S. Johnson, J. T. Vaughey, K. Amine, M. M. Thackeray. "The effects of acid treatment on the electrochemical properties of 0.5Li2MnO3･0.5LiNi0.44Co0.25Mn0.31O2 electrodes in lithium cells", Journal of The Electrochemical Society, 153, A1186-A1192 (2006).
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96. 100. J. S. Kim, C. S. Johnson, J. T. Vaughey, M. M. Thackeray. "Pre-conditioned layered electrodes for lithium batteries", Journal of Power Sources, 153, 258-264 (2006).
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97. 101. J. Zheng, S. N. Deng, Z. C. Shi, H. J. Xu, H. Xu, Y. F. Deng, Z. Zhang, G. H. Chen. "The effects of persulfate treatment on the electrochemical properties of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material", Journal of Power Sources, 221, 108-113 (2013).
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98. 102. D. Y. W. Yu, K. Yanagida, H. Nakamura. "Surface Modification of Li-Excess Mn-based Cathode Materials", Journal of The Electrochemical Society, 157, A1177-A1182 (2010).
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99. 103. S. H. Kang, M. M. Thackeray. "Stabilization of xLi2MnO3･(1-x)LiMO2 electrode surfaces (M = Mn, Ni, Co) with mildly acidic, fluorinated solutions", Journal of The Electrochemical Society, 155, A269-A275 (2008).
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100. 104. Y. Wu, A. Manthiram. "High capacity, surface-modified layered Li[Li(1-x)/3Mn(2-x)/3Nix/3Cox/3]O2 cathodes with low irreversible capacity loss", Electrochemical and Solid State Letters, 9, A221-A224 (2006).
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101. 105. W. C. West, J. Soler, M. C. Smart, B. V. Ratnakumar, S. Firdosy, V. Ravi, M. S. Anderson, J. Hrbacek, E. S. Lee, A. Manthiram. "Electrochemical Behavior of Layered Solid Solution Li2MnO3-LiMO2 (M = Ni, Mn, Co) Li-Ion Cathodes with and without Alumina Coatings", Journal of The Electrochemical Society, 158, A883-A889 (2011).
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102. 106. J. Liu, A. Manthiram. "Functional surface modifications of a high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode", Journal of Materials Chemistry, 20, 3961-3967 (2010).
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103. 107. S. H. Guo, H. J. Yu, P. Liu, X. Z. Liu, D. Li, M. W. Chen, M. Ishida, H. S. Zhou. "Surface coating of lithium-manganese-rich layered oxides with delaminated MnO2 nanosheets as cathode materials for Li-ion batteries", Journal of Materials Chemistry A, 2, 4422-4428 (2014).
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104. 108. F. Wu, N. Li, Y. F. Su, H. Q. Lu, L. J. Zhang, R. An, Z. Wang, L. Y. Bao, S. Chen. "Can surface modification be more effective to enhance the electrochemical performance of lithium rich materials?", Journal of Materials Chemistry, 22, 1489-1497 (2012).
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105. 109. E. S. Han, Y. P. Li, L. Z. Zhu, L. Zhao. "The effect of MgO coating on Li1.17Mn0.48Ni0.23Co0.12O2 cathode material for lithium ion batteries", Solid State Ionics, 255, 113-119 (2014).
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106. 110. Z. Y. Wang, E. Z. Liu, L. C. Guo, C. S. Shi, C. N. He, J. J. Li, N. Q. Zhao. "Cycle performance improvement of Li-rich layered cathode material Li[Li0.2Mn0.54Ni0.13Co0.13]O2 by ZrO2 coating", Surface & Coatings Technology, 235, 570-576 (2013).
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107. 112. X. F. Zhang, I. Belharouak, L. Li, Y. Lei, J. W. Elam, A. M. Nie, X. Q. Chen, R. S. Yassar, R. L. Axelbaum. "Structural and Electrochemical Study of Al2O3 and TiO2 Coated Li1.2Ni0.13Mn0.54Co0.13O2 Cathode Material Using ALD", Advanced Energy Materials, 3, 1299-1307 (2013).
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108. 113. Z. Y. Wang, E. Z. Liu, C. N. He, C. S. Shi, J. J. Li, N. Q. Zhao. "Effect of amorphous FePO4 coating on structure and electrochemical performance of Li1.2Ni0.13Co0.13Mn0.54O2 as cathode material for Li-ion batteries", Journal of Power Sources, 236, 25-32 (2013).
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109. 114. Y. Wu, A. V. Murugan, A. Manthiram. "Surface modification of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathodes by AlPO4", Journal of The Electrochemical Society, 155, A635-A641 (2008).
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110. 115. Y. K. Sun, M. J. Lee, C. S. Yoon, J. Hassoun, K. Amine, B. Scrosati. "The Role of AlF3 Coatings in Improving Electrochemical Cycling of Li-Enriched Nickel-Manganese Oxide Electrodes for Li-Ion Batteries", Advanced Materials, 24, 1192-1196 (2012).
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111. 116. F. Amalraj, M. Talianker, B. Markovsky, L. Burlaka, N. Leifer, G. Goobes, E. M. Erickson, O. Haik, J. Grinblat, E. Zinigrad, D. Aurbach, J. K. Lampert, J. Y. Shin, M. Schulz-Dobrick, A. Garsuch. "Studies of Li and Mn-Rich Lix[MnNiCo]O2 Electrodes: Electrochemical Performance, Structure, and the Effect of the Aluminum Fluoride Coating", Journal of The Electrochemical Society, 160, A2220-A2233 (2013).
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112. 117. H. Deng, I. Belharouak, C. S. Yoon, Y. K. Sun, K. Amine. "High Temperature Performance of Surface-Treated Li1.1(Ni0.15Co0.1Mn0.55)O1.95 Layered Oxide", Journal of The Electrochemical Society, 157, A1035-A1039 (2010).
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113. 118. C. R. Wu, X. P. Fang, X. W. Guo, Y. Mao, J. Ma, C. C. Zhao, Z. X. Wang, L. Q. Chen. "Surface modification of Li1.2Mn0.54Co0.13Ni0.13O2 with conducting polypyrrole", Journal of Power Sources, 231, 44-49 (2013).
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114. 119. D. Ahn, Y. M. Koo, M. G. Kim, N. Shin, J. Park, J. Eom, J. Cho, T. J. Shin. "Polyaniline Nanocoating on the Surface of Layered Li[Li0.2Co0.1Mn0.7]O2 Nanodisks and Enhanced Cyclability as a Cathode Electrode for Rechargeable Lithium-Ion Battery", Journal of Physical Chemistry C, 114, 3675-3680 (2010).
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115. 120. C. Arbizzani, A. Balducci, M. Mastragostino, M. Rossi, F. Soavi. "Characterization and electrochemical performance of Li-rich manganese oxide spinel/poly(3,4-ethylenedioxythiophene) as the positive electrode for lithium-ion batteries", Journal of Electroanalytical Chemistry, 553, 125-133 (2003).
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116. 121. J. Liu, Q. Y. Wang, B. Reeja-Jayan, A. Manthiram. "Carbon-coated high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathodes", Electrochemistry Communications, 12, 750-753 (2010).
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117. 122. L. N. Cong, X. G. Gao, S. C. Ma, X. Guo, Y. P. Zeng, L. H. Tai, R. S. Wang, H. M. Xie, L. Q. Sun. "Enhancement of electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 by surface modification with Li4Ti5O12", Electrochimica Acta, 115, 399-406 (2014).
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118. 123. Q. Q. Qiao, H. Z. Zhang, G. R. Li, S. H. Ye, C. W. Wang, X. P. Gao. "Surface modification of Li-rich layered Li(Li0.17Ni0.25Mn0.58)O2 oxide with Li-Mn-PO4 as the cathode for lithium-ion batteries", Journal of Materials Chemistry A, 1, 5262-5268 (2013).
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119. 124. B. Liu, Q. Zhang, S. C. He, Y. C. Sato, J. W. Zheng, D. C. Li. "Improved electrochemical properties of Li1.2Ni0.18Mn0.59Co0.03O2 by surface modification with LiCoPO4", Electrochimica Acta, 56, 6748-6751 (2011).
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120. 125. C. C. Wang, A. Manthiram. "Influence of cationic substitutions on the first charge and reversible capacities of lithium-rich layered oxide cathodes", Journal of Materials Chemistry A, 1, 10209-10217 (2013).
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121. 126. Y. K. Sun, M. G. Kim, S. H. Kang, K. Amine. "Electrochemical performance of layered Li[Li0.15Ni0.275-xMgxMn0.575]O2 cathode materials for lithium secondary batteries", Journal of Materials Chemistry, 13, 319-322 (2003).
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122. 127. J. H. Park, J. Lim, J. Yoon, K. S. Park, J. Gim, J. Song, H. Park, D. Im, M. Park, D. Ahn, Y. Paik, J. Kim. "The effects of Mo doping on 0.3Li[Li0.33Mn0.67]O2･0.7Li[Ni0.5Co0.2Mn0.3]O2 cathode material", Dalton Transactions, 41, 3053-3059 (2012).
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123. 128. G. Singh, R. Thomas, A. Kumar, R. S. Katiyar. "Electrochemical Behavior of Cr- Doped Composite Li2MnO3-LiMn0.5Ni0.5O2 Cathode Materials", Journal of The Electrochemical Society, 159, A410-A420 (2012).
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124. 129. H. J. Yu, H. S. Zhou. "Initial Coulombic efficiency improvement of the Li1.2Mn0.567Ni0.166Co0.067O2 lithium-rich material by ruthenium substitution for manganese", Journal of Materials Chemistry, 22, 15507-15510 (2012).
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125. 130. Z. Li, N. A. Chernova, J. J. Feng, S. Upreti, F. Omenya, M. S. Whittingham. "Stability and Rate Capability of Al Substituted Lithium-Rich High-Manganese Content Oxide Materials for Li-Ion Batteries", Journal of The Electrochemical Society, 159, A116-A120 (2012).
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126. 131. L. F. Jiao, M. Zhang, H. T. Yuan, M. Zhao, H. Guo, W. Wang, X. Di Zhou, Y. M. Wang. "Effect of Cr doping on the structural, electrochemical properties of Li[Li0.2Ni0.2-x/2Mn0.6-x/2Crx]O2 (x=0, 0.02, 0.04, 0.06, 0.08) as cathode materials for lithium secondary batteries", Journal of Power Sources, 167, 178-184 (2007).
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127. 132. Z. Q. Deng, A. Manthiram. "Influence of Cationic Substitutions on the Oxygen Loss and Reversible Capacity of Lithium-Rich Layered Oxide Cathodes", Journal of Physical Chemistry C, 115, 7097-7103 (2011).
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128. 133. H. Deng, I. Belharouak, H. Wu, D. Dambournet, K. Amine. "Effect of Cobalt Incorporation and Lithium Enrichment in Lithium Nickel Manganese Oxides", Journal of The Electrochemical Society, 157, A776-A781 (2010).
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129. 134. H. X. Li, L. Z. Fan. "Effects of fluorine substitution on the electrochemical performance of layered Li-excess nickel manganese oxides cathode materials for lithium-ion batteries", Electrochimica Acta, 113, 407-411 (2013).
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130. 135. S. H. Kang, K. Amine. "Layered Li(Li0.2Ni0.15+0.5zCo0.10Mn0.55-0.5z)O2-zFz cathode materials for Li-ion secondary batteries", Journal of Power Sources, 146, 654-657 (2005).
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131. 136. S. W. Cho, G. O. Kim, K. S. Ryu. "Sulfur anion doping and surface modification with LiNiPO4 of a Li[Co0.1Ni0.15Li0.2Mn0.55]O2 cathode material for Li-ion batteries", Solid State Ionics, 206, 84-90 (2012).
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132. 137. S. K. Martha, J. Nanda, G. M. Veith, N. J. Dudney. "Electrochemical and rate performance study of high-voltage lithium-rich composition: Li1.2Mn0.525Ni0.175Co0.1O2", Journal of Power Sources, 199, 220-226 (2012).
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133. 138. A. Ito, D. Li, Y. Ohsawa, Y. Sato. "A new approach to improve the high-voltage cyclic performance of Li-rich layered cathode material by electrochemical pre-treatment", Journal of Power Sources, 183, 344-346 (2008).
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134. 139. A. R. Armstrong, N. Dupre, A. J. Paterson, C. P. Grey, P. G. Bruce. "Combined neutron diffraction, NMR, and electrochemical investigation of the layered-to-spinel transformation in LiMnO2", Chemistry of Materials, 16, 3106-3118 (2004).
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135. 140. B. Xu, D. N. Qian, Z. Y. Wang, Y. S. L. Meng. "Recent progress in cathode materials research for advanced lithium ion batteries", Materials Science & Engineering R-Reports, 73, 51-65 (2012).
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136. 141. M. Gu, I. Belharouak, J. M. Zheng, H. M. Wu, J. Xiao, A. Genc, K. Amine, S. Thevuthasan, D. R. Baer, J. G. Zhang, N. D. Browning, J. Liu, C. M. Wang. "Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries", Acs Nano, 7, 760-767 (2013).
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137. 142. J. M. Zheng, M. Gu, J. Xiao, P. J. Zuo, C. M. Wang, J. G. Zhang. "Corrosion/Fragmentation of Layered Composite Cathode and Related Capacity/Voltage Fading during Cycling Process", Nano Letters, 13, 3824-3830 (2013).
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138. 144. X. Y. Liu, J. L. Liu, T. Huang, A. S. Yu. "CaF2-coated Li1.2Mn0.54Ni0.13Co0.13O2 as cathode materials for Li-ion batteries", Electrochimica Acta, 109, 52-58 (2013).
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139. 145. J. H. Kim, M. S. Park, J. H. Song, D. J. Byun, Y. J. Kim, J. S. Kim. "Effect of aluminum fluoride coating on the electrochemical and thermal properties of 0.5Li2MnO3･0.5LiNi0.5Co0.2Mn0.3O2 composite material", Journal of Alloys and Compounds, 517, 20-25 (2012).
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140. 146. M. Bettge, Y. Li, K. Gallagher, Y. Zhu, Q. L. Wu, W. Q. Lu, I. Bloom, D. P. Abraham. "Voltage Fade of Layered Oxides: Its Measurement and Impact on Energy Density", Journal of The Electrochemical Society, 160, A2046-A2055 (2013).
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141. 147. J. R. Croy, D. Kim, M. Balasubramanian, K. Gallagher, S. H. Kang, M. M. Thackeray. "Countering the Voltage Decay in High Capacity xLi2MnO3･(1-x)LiMO2 Electrodes (M=Mn, Ni, Co) for Li+-Ion Batteries", Journal of The Electrochemical Society, 159, A781-A790 (2012).
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142. 148. D. Kim, G. Sandi, J. R. Croy, K. G. Gallagher, S. H. Kang, E. Lee, M. D. Slater, C. S. Johnson, M. M. Thackeray. "Composite 'Layered-Layered-Spinel' Cathode Structures for Lithium-Ion Batteries", Journal of The Electrochemical Society, 160, A31-A38 (2013).
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143. 149. X. K. Yang, D. Wang, R. Z. Yu, Y. S. Bai, H. B. Shu, L. Ge, H. P. Guo, Q. L. Wei, L. Liu, X. Y. Wang. "Suppressed capacity/voltage fading of high-capacity lithium-rich layered materials via the design of heterogeneous distribution in the composition", Journal of Materials Chemistry A, 2, 3899-3911 (2014).
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144. 150. M. N. Ates, S. Mukerjee, K. M. Abraham. "A Li-Rich Layered Cathode Material with Enhanced Structural Stability and Rate Capability for Li-on Batteries", Journal of The Electrochemical Society, 161, A355-A363 (2014).
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145. 151. K. S. Lee, S. T. Myung, H. J. Bang, S. J. Chung, Y. K. Sun. "Co-precipitation synthesis of spherical Li1.05M0.05Mn1.9O4 (M = Ni, Mg, Al) spinel and its application for lithium secondary battery cathode", Electrochimica Acta, 52, 5201-5206 (2007).
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146. 152. Z. H. Lu, J. R. Dahn. "Structure and electrochemistry of layered Li[CrxLi(1/3-x3)Mn(2/3-2x/3)]O2", Journal of The Electrochemical Society, 149, A1454-A1459 (2002).
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147. 153. D. Y. W. Yu, K. Yanagida, Y. Kato, H. Nakamura. "Electrochemical Activities in Li2MnO3", Journal of The Electrochemical Society, 156, A417-A424 (2009).
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148. 154. H. X. Deng, I. Belharouak, Y. K. Sun, K. Amine. "LixNi0.25Mn0.75Oy (0.5 ≤ x ≤ 2, 2 ≤ y ≤ 2.75) compounds for high-energy lithium-ion batteries", Journal of Materials Chemistry, 19, 4510-4516 (2009).
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149. 155. S. Zhang, C. Deng, B. L. Fu, S. Y. Yang, L. Ma. "Synthetic optimization of spherical Li[Ni1/3Mn1/3Co1/3]O2 prepared by a carbonate co-precipitation method", Powder Technology, 198, 373-380 (2010).
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