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      "text": "consequence of the lattice breakdown and vacancy condensation upon removal of lithium ions. The AlF 3 -coating can partially relieve the spinel formation in the layered structure during cycling, resulting in a slower capacity decay. However, the AlF 3 -coating on the layered structure cannot ultimately stop the spinel formation. The observation of structure transition characteristics discussed in this paper provides direct explanation for the observed gradual capacity loss and poor rate performance of the layered composite. It also provides clues about how to improve the materials structure in order to improve electrochemical performance.",
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      "text": "ABSTRACT Pristine Li-rich layered cathodes, such as Li 1.2 Ni 0.2 Mn0.6 O2 and Li 1.2 Ni 0.1 Mn0.525 -Co0.175 O2 , were identi fi ed to exist in two di ff erent structures: LiMO 2 R 3 m and Li2MO3 C 2/ m phases. Upon 300 cycles of charge/discharge, both phases gradually transform to the spinel structure. The transition from LiMO 2 R 3 m to spinel is accomplished through the migration of transition metal ions to the Li site without breaking down the lattice, leading to the formation of mosaic structured spinel grains within the parent particle. In contrast, transition from Li2MO3 C 2/ m to spinel involves removal of Li þ and O 2 -, which produces large lattice strain and leads to the breakdown of the parent lattice. The newly formed spinel grains show random orientation within the same particle. Cracks and pores were also noticed within some layered nanoparticles after cycling, which is believed to be the",
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      "text": "L i-ion batteries have been widely used as an energy storage device for modern electric devices, grid application, and renewable energy. 1 \u0000 7 Cathodes with a layered structure such as Li1.2Ni0.2Mn0.6O2 (LNMO) andLi1.2Ni0.1Mn0.525Co0.175O2(LNMCO) can provide much higher capacity than the traditional cathode materials such as LiCoO2 and LiMn2O4 spinel. 8 \u0000 12 Therefore, these layered structures are one of the most promising candidates for future heavy duty applications such as hybrid and electric vehicles. However, the application of these materials faces three fundamental challenges: (1) voltage instability, (2) capacity fading, and (3) slow charge/discharge rate. Collective experimental observations indicate these challenges are closely related to the structural characteristics of these materials, suchasthecrystal structure, spatial distribution",
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      "text": "of cations, and phase stability upon lithium extraction and insertion. Structurally, these layered structures are often composed of the intergrowth of LiMO2 R 3 m and Li2MO3 C 2/ m phases. 7,13 Nevertheless, it is not clear how each individual phase a ff ects the performance of these materials. Further, the cations are not necessarily uniformly distributed at nanometer scale. Recently, Gu et al . 7 reported a nanoscale phase separation caused by the preferential segregation of Ni atoms on the particle surface and boundaries in the layered lithium nickel manganese oxide cathode materials. They further predicted that the formation of the Ni-rich surface layer would a ff ect the di ff usion of Li ions, and thus possibly have an impact on the rate performance of this cathode. 7 Accompanying the extraction of Li from the Li2MO3 phase at the 4.5 V voltage plateau is",
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      "text": "* Address correspondence to Chongmin.Wang@pnnl.gov.",
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      "text": "Received for review October 31, 2012 and accepted December 13, 2012.",
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      "text": "the release of oxygen and Li þ (removal of the Li2O part). 2 However, the e ff ect of the removal of the Li2O part on the lattice stability has not been established. The layered-to-spinel transformation has long been postulated as an important factor to account for the capacity fading and poor rate performance of the layered structure materials. 2,9,10,13 \u0000 17 However, it is not clear where the spinel phase nucleates and how the spinel phase grows on the consumption of the layered structured phase. The answers to these questions critically depends on the atomic level structural and chemical analysis of materials and their correlation with the cyclic performance of the battery. On the basis of atomic scale Z -contrast imaging, Xu et al . have found that the migration of transition metal (TM) cations into the Li layers can initiate the formation of spinel near the particle surface region. 15 Apparently, a far more detailed microscopic understanding of the phase transformation characteristics in these layered structures will lead to tailoring of the materials structure for better electrochemical performance.",
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      "text": "Figure 8. (a \u0000 d) Cycled LNMO and (e) LNMCO samples showing porosity formation after 60 cycles. (a) Z -contrast image; (b) bright fi eld image; (c) higher magni fi cation Z-contrast and (d) bright fi eld image showing the contrast comparison of the pores in LNMO sample; (e) STEM Zcontrast image and EDS maps of cycled LNMCO sample. Thescale bar in panel e is 30 nm and can be applied to all the elemental maps therein.",
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      "text": "Acknowledgment. The research described in this paper is part of the Chemical Imaging Initiative at Paci fi c Northwest National Laboratory (PNNL). It was conducted under the Laboratory Directed Research and Development Program at PNNL, a multiprogram national laboratory operated by Battelle under Contract DE-AC05-76RLO1830 for the U.S. Department of Energy (DOE). The work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scienti fi c user facility sponsored by DOE's O ffi ce of Biological and Environmental Research and located at PNNL. J. Zhang and J. Xiao would like to acknowledge the support of the Assistant Secretary for Energy E ffi ciency and Renewable Energy, O ffi ce of Vehicle Technologies of DOE under Contract No. DE-AC02-05CH11231, Subcontract No. 18769 under the Batteries for Advanced Transportation Technologies (BATT) program. J. Liu would like to acknowledge the support of the DOE Offi ce of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Award KC020105-FWP12152. I. Belharouak and K. Amine would like to acknowledge the support from DOE's Freedom CAR and Vehicle Technologies O ffi ce.",
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      "text": "Armstrong, A. R.; Bruce, P. G. Synthesis of Layered LiMnO2 as an Electrode for Rechargeable Lithium Batteries. Nature 1996 , 381 , 499 -500.",
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