Structural, electrochemical and thermal stability investigations on LiNi0.5−xAl2xMn1.5−xO4 (0 ≤ 2x ≤ 1.0) as 5 V cathode materials

Zhong, Guobin; Wang, Y.Y.; Zhao, Xuejuan; Wang, Q.S.; Yu, Yan; Chen, C.H.

doi:10.1016/j.jpowsour.2012.05.108

Cited by 73 publications

(34 citation statements)

References 35 publications

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“…. Meanwhile, the voltage difference between the anodic and cathodic peaks reflects the degree of polarization of the electrode, and is also affected by the degree of disorder of the cations and the extraction/rein-sertion rate of Li + in the spinel structure [45,46]. To understand the reversibility of the electrode material, we calculated the voltage differences between the two split peaks near 4.7 V. Results are shown in Table 1.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and electrochemical performance of Sn-doped LiNi0.5Mn1.5O4 cathode material for high-voltage lithium-ion batteries

Hao

et al. 2017

Sci. China Mater.

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LiNi0.5Mn1.5−xSnxO4 (0 ≤ x ≤ 0.1) cathode materials with uniform and fine particle sizes were successfully synthesized by a two-step calcination of solid-state reaction method. As the cathode materials for lithium ion batteries, the LiNi0.5Mn1.48Sn0.02O4 shows the highest specific capacity and cycle stability. In the potential range of 3.5-4.9 V at room temperature, LiNi0.5Mn1.48Sn0.02O4 composite material shows a discharge capacity of more than 117 mA h g −1 at 0.1 C, while the corresponding discharge capacity of undoped LiNi0.5Mn1.5O4 is only 101 mA h g −1 . Moreover, in cycle performance, all the LiNi0.5Mn1.5−xSnxO4 (0 ≤ x ≤ 0.1) samples show better capacity retention than the undoped LiNi0.5Mn1.5O4 at 1 C rate after 100 cycles. Especially, for the LiNi0.5Mn1.5O4, the discharge capacity after 100 cycles is 90 mA h g −1 , while the corresponding discharge capacities of the undoped LiNi0.5Mn1.5O4 is only 56.1 mA h g −1 . The significantly enhanced DLi + and the enlarged electronic conductivity make the Sn-doped spinel LiNi0.5Mn1.5O4 material present even more excellent electrochemical performances. These results reveal that Sn-doping is an effective way to improve electrochemical performances of LiNi0.5Mn1.5O4.

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Section: Resultsmentioning

confidence: 99%

Synthesis and electrochemical performance of Sn-doped LiNi0.5Mn1.5O4 cathode material for high-voltage lithium-ion batteries

Hao

et al. 2017

Sci. China Mater.

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“…The disordering of Ni/Mn can be typically increased by introducing the Mn 3+ ions that can be controlled by experimental conditions 6, 20 or that can be controlled by the doping of aliovalent metals instead of Ni because the doping can increase the quantity of Mn 3+ ions to meet charge neutrality in the spinel 4, 14, 21–23 . Therefore, the LNMO spinel obtained from these approaches always has both the disordering of Ni/Mn and Mn 3+ ions.…”

Section: Introductionmentioning

confidence: 99%

Understanding the cation ordering transition in high-voltage spinel LiNi0.5Mn1.5O4 by doping Li instead of Ni

Lee

Dupré

Avdeev

et al. 2017

Sci Rep

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We determined how Li doping affects the Ni/Mn ordering in high-voltage spinel LiNi0.5Mn1.5O4(LNMO) by using neutron diffraction, TEM image, electrochemical measurements, and NMR data. The doped Li occupies empty octahedral interstitials (16c site) before the ordering transition, and can move to normal octahedral sites (16d (4b) site) after the transition. This movement strongly affects the Ni/Mn ordering transition because Li at 16c sites blocks the ordering transition pathway and Li at 16d (4b) sites affects electrostatic interactions with transition metals. As a result, Li doping increases in the Ni/Mn disordering without the effect of Mn3+ ions even though the Li-doped LNMO undergoes order-disorder transition at 700 °C. Li doping can control the amount of Ni/Mn disordering in the spinel without the negative effect of Mn3+ ions on the electrochemical property.

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“…in the spinel structure must be kept at an appropriate level to curb capacity-fading at elevated temperature. There have been several strategies proposed in the literature to minimize capacity-fading in LMO, which include the following; (i) surface-coating of LMO with metal oxides, 18,19 (ii) coating LMO with specific metals (Bi, Pb, La, Ba, Zr, Y, Sr, Zn and Mg), 20 (iii) simultaneous doping with aluminium and fluorine, 21 (iv) the surface-treatment process of nickel-doped LMO (LMNO) powder utilizing two strong acids, hydrofluoric acid (HF) and phosphoric acid (H 3 PO 4 ), 22 (v) coating lithium-rich LMO with LMNO, 23 (vi) co-doping of LMO with aluminium and nickel via the so-called thermopolymerisation method with acrylic acid, 24 and (vii) the addition of mixed additives (bis(dialkylamino)naphthalene and vinylene carbonate) to the electrolyte. 25 On the other hand, the research groups of Manthiram 26 and Chen 27 have also demonstrated that LMNO with predominant surface {111} facets exhibited improved cycling performance as exposed {111} facets allow the formation of a thinner solid electrolyte interphase (SEI) than other facets.…”

Section: Introductionmentioning

confidence: 99%

Microwave-enhanced electrochemical cycling performance of the LiNi_0.2Mn_1.8O₄ spinel cathode material at elevated temperature

Raju

Nkosi

Elumalai

et al. 2016

Phys. Chem. Chem. Phys.

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The well-established poor electrochemical cycling performance of the LiMn2O4 (LMO) spinel cathode material for lithium-ion batteries at elevated temperature stems from the instability of the Mn(3+) concentration. In this work, a microwave-assisted solid-state reaction has been used to dope LMO with a very low amount of nickel (i.e., LiNi0.2Mn1.8O4, herein abbreviated as LMNO) for lithium-ion batteries from Mn3O4 which is prepared from electrolytic manganese oxide (EMD, γ-MnO2). To establish the impact of microwave irradiation on the electrochemical cycling performance at an elevated temperature (60 °C), the Mn(3+) concentration in the pristine and microwave-treated LMNO samples was independently confirmed by XRD, XPS, (6)LiMAS-NMR and electrochemical studies including electrochemical impedance spectroscopy (EIS). The microwave-treated sample (LMNOmic) allowed for the clear exposure of the {111} facets of the spinel, optimized the Mn(3+) content, promoting structural and cycle stability at elevated temperature. At room temperature, both the pristine (LMNO) and microwave-treated (LMNOmic) samples gave comparable cycling performance (>96% capacity retention and ca. 100% coulombic efficiency after 100 consecutive cycling). However, at an elevated temperature (60 °C), the LMNOmic gave an improved cycling stability (>80% capacity retention and ca. 90% coulombic efficiency after 100 consecutive cycling) compared to the LMNO. For the first time, the impact of microwave irradiation on tuning the average manganese redox state of the spinel material to enhance the cycling performance of the LiNi0.2Mn1.8O4 at elevated temperature and lithium-ion diffusion kinetics has been clearly demonstrated.

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Structural, electrochemical and thermal stability investigations on LiNi0.5−xAl2xMn1.5−xO4 (0 ≤ 2x ≤ 1.0) as 5 V cathode materials

Cited by 73 publications

References 35 publications

Synthesis and electrochemical performance of Sn-doped LiNi0.5Mn1.5O4 cathode material for high-voltage lithium-ion batteries

Synthesis and electrochemical performance of Sn-doped LiNi0.5Mn1.5O4 cathode material for high-voltage lithium-ion batteries

Understanding the cation ordering transition in high-voltage spinel LiNi0.5Mn1.5O4 by doping Li instead of Ni

Microwave-enhanced electrochemical cycling performance of the LiNi_0.2Mn_1.8O₄ spinel cathode material at elevated temperature

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Structural, electrochemical and thermal stability investigations on LiNi0.5−xAl2xMn1.5−xO4 (0 ≤ 2x ≤ 1.0) as 5 V cathode materials

Cited by 73 publications

References 35 publications

Synthesis and electrochemical performance of Sn-doped LiNi0.5Mn1.5O4 cathode material for high-voltage lithium-ion batteries

Synthesis and electrochemical performance of Sn-doped LiNi0.5Mn1.5O4 cathode material for high-voltage lithium-ion batteries

Understanding the cation ordering transition in high-voltage spinel LiNi0.5Mn1.5O4 by doping Li instead of Ni

Microwave-enhanced electrochemical cycling performance of the LiNi0.2Mn1.8O4 spinel cathode material at elevated temperature

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Microwave-enhanced electrochemical cycling performance of the LiNi_0.2Mn_1.8O₄ spinel cathode material at elevated temperature