Synthesis and characterization of the metal-doped high-voltage spinel LiNi0.5Mn1.5O4 by mechanochemical process

Oh, Si Hyoung; Jeon, Sang Hoon; Cho, Won Il; Kim, Chang Sam; Cho, Byung Won

doi:10.1016/j.jallcom.2006.10.153

Cited by 74 publications

(44 citation statements)

References 24 publications

(51 reference statements)

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“…Below the surface film overlayer, Mn retained its original chemical state and structure. We note that the Mn 2p spectra collected from cycled positive electrodes with excitation energy of 2493 eV have a contribution from the X-ray induced P KLL Auger line, due to the presence of LiPF 6 and Li x PF y O z species, as previously noted.…”

Section: Mn 2p Region-as Shown Insupporting

confidence: 78%

“…In addition, Figure 5 displays a P contribution, which corresponds to LiPF 6 . The intensity of Li x PF y O z relative to that of LiPF 6 with Mg X-rays significantly decreased when the excitation energy increased to 2493 and 3498 eV, indicating that the Li x PF y O z component resides closer to the surface than the LiPF 6 component. Figure 6, the Ni 2p spectra of the pristine LNMO positive electrode are similar to that of Ni in LiNi 0.5 Mn 0.5 O 2 , in both cases with binding energy near 854.8 eV and Ni is present as Ni 2+ .…”

Section: F 1s and P 2p Regions-as Shown Inmentioning

confidence: 95%

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Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Mansour

Kwabi

Quinlan

et al. 2016

J. Electrochem. Soc.

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X-ray photoelectron spectroscopy (XPS) was used to investigate the surface chemistry of high voltage spinel, LiNi 0.5 Mn 1.5 O 4 (LNMO) positive electrodes cycled 5 and 10 times in Li-cells with 1 M LiPF 6 in (3:7) EC:DMC. The XPS spectra were collected using conventional Mg X-rays with energy of 1253.6 eV as well as synchrotron X-rays with energies of 2493.6 and 3498.4 eV in order to examine the depth distribution of various surface chemical species induced during cycling. The XPS spectra revealed a 5 -10 nm surface layer of organic and Li x PF y O z -type species formed as result of electrolyte decomposition, and a comparatively thinner layer composed of transition metal fluorides and LiF. These results suggest that electrolyte decomposition is a major contributor to parasitic reactions in LNMO battery electrochemistry. Limiting electrolyte decomposition with the use of solvents with wide electrochemical stability windows thus comprises a promising strategy for ensuring the practical feasibility of high voltage spinel materials in future Li-ion systems. Rechargeable lithium-ion batteries (LIBs) are among the widest used energy sources for portable electronic devices, but are currently being considered for more energy-dense applications such as electric vehicles and short-term grid support. In order to realize these possibilities, gravimetric energy densities of typical LIBs, which currently provide 400-550 Wh/kg need to be improved. LiNi 0.5 Mn 1.5 O 4 (LNMO) is a particularly promising positive electrode material in this regard, as it operates at an exceptionally high voltage of 4.8 V vs Li + /Li, 1 resulting in an energy density of ∼706 Wh/kg based on a theoretical capacity of 147 mAh/g for 1e − transfer. 2 Such a high voltage is however above the potential at which most LIB electrodes, cell components and electrolytes decompose (>4.2 V vs Li + /Li), and results in the formation of highly resistive parasitic species that hamper battery reversibility and cycle life.In order to design LIBs that are chemically stable enough for practical application, a strong fundamental understanding of electrolyte decomposition and side product formation mechanisms is required. In positive LIB electrodes, battery cycling typically results in an electrode-electrolyte interface (EEI), the study of which can yield mechanistic insights into particularly critical parasitic reaction pathways responsible for poor electrochemical performance.3 Thus, understanding the structure and composition of the surface EEI in LNMObased positive electrodes is key to their commercial realization.Previous studies exploring LNMO performance degradation during cycling have explored the influence of stoichiometry, 4 cation ordering, 4,5 doping 6 and particle morphology. 5,7,8 There have been relatively fewer studies exploring EEI formation in detail, likely owing to the difficulty of characterizing thin layers (typically < 20 nm) of product. Using Raman and Electrochemical Impedance Spectroscopy (EIS) measurements, Aurbach et al. 9 suggested that LNMO...

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Section: Mn 2p Region-as Shown Insupporting

confidence: 78%

Section: F 1s and P 2p Regions-as Shown Inmentioning

confidence: 95%

Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Mansour

Kwabi

Quinlan

et al. 2016

J. Electrochem. Soc.

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“…The high-voltage spinels with various nominal compositions of LiNi 0.5−x Mn 1.5−y M x+y O 2 , were prepared by mechanochemical method [10,22], in which planetary-type ball mill was adopted for the mechanical activation of the starting materials. After that, the ball-milled powder was collected and subjected to further two-step heat treatment at 600 • C for 8 h in air and subsequently, at 800-900 • C for 12-24 h in the flowing oxygen atmosphere.…”

Section: Methodsmentioning

confidence: 99%

Structural and electrochemical investigations on the LiNi0.5−xMn1.5−yMx+yO4 (M=Cr, Al, Zr) compound for 5V cathode material

Chung

Jeon

et al. 2009

Journal of Alloys and Compounds

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“…Mechanochemical process was performed in a similar manner to our previous works using a planetary mill (FRITSCH Pulverisette 5, 300 rpm, 3 h), followed by the heat treatment in a box furnace at 600°C for 5 h. [7][8][9][10][11] The ball-to-powder weight ratio was optimized at the ratio of 20:1. Mn 2 V 2 O 7 , Li 2 CO 3 (Aldrich), and (NH 4 ) 2 HPO 4 (Aldrich) were mixed with the stoichiometric ratio of 1:2.5:5 to yield the Li 3 V 2 (PO 4 ) 3 -LiMnPO 4 composite with a mole ratio of Li 3 V 2 (PO 4 ) 3 : LiMnPO 4 = 1:2.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Electrochemical Properties of Li₃V₂(PO₄)₃-LiMnPO₄Composite Cathode Material for Lithium-ion Batteries

Yun

Kim

Cho

et al. 2013

Bulletin of the Korean Chemical Society

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Carbon-coated Li 3 V 2 (PO 4 ) 3 -LiMnPO 4 composite cathode materials are first reported in this work, prepared by the mechanochemical process with a complex metal oxide as the precursor and sucrose as the carbon source. X-ray diffraction pattern of the composite material indicates that both olivine LiMnPO 4 and monoclinic Li 3 V 2 (PO 4 ) 3 co-exist. We further investigated the electrochemical properties of our Li 3 V 2 (PO 4 ) 3 -LiMnPO 4 composite cathode materials using galvanostatic charging/discharging tests, where our Li 3 V 2 (PO 4 ) 3 -LiMnPO 4 composite electrode materials exhibit the charge/discharge efficiency of 91.9%, while Li 3 V 2 (PO 4 ) 3 and LiMnPO 4 exhibit the efficiency of 87.7 and 86.7% in the first cycle. The composites display unique electrochemical performances in terms of overvoltage and cycle stability, displaying a reduced gap of 141.6 mV between charge and discharge voltage and 95.0% capacity efficiency after 15 th cycles.

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Synthesis and characterization of the metal-doped high-voltage spinel LiNi0.5Mn1.5O4 by mechanochemical process

Cited by 74 publications

References 24 publications

Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Structural and electrochemical investigations on the LiNi0.5−xMn1.5−yMx+yO4 (M=Cr, Al, Zr) compound for 5V cathode material

Synthesis and Electrochemical Properties of Li₃V₂(PO₄)₃-LiMnPO₄Composite Cathode Material for Lithium-ion Batteries

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Synthesis and characterization of the metal-doped high-voltage spinel LiNi0.5Mn1.5O4 by mechanochemical process

Cited by 74 publications

References 24 publications

Probing the Electrode-Electrolyte Interface in Cycled LiNi0.5Mn1.5O4by XPS Using Mg and Synchrotron X-rays

Probing the Electrode-Electrolyte Interface in Cycled LiNi0.5Mn1.5O4by XPS Using Mg and Synchrotron X-rays

Structural and electrochemical investigations on the LiNi0.5−xMn1.5−yMx+yO4 (M=Cr, Al, Zr) compound for 5V cathode material

Synthesis and Electrochemical Properties of Li3V2(PO4)3-LiMnPO4Composite Cathode Material for Lithium-ion Batteries

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Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Synthesis and Electrochemical Properties of Li₃V₂(PO₄)₃-LiMnPO₄Composite Cathode Material for Lithium-ion Batteries