Electrochemical performance of LiNi0.5Mn1.5O4 composite electrodes featuring carbons and reduced graphene oxide

Monaco, Simone; Giorgio, Francesca De; Col, L. Da; Riché, M.; Arbizzani, Catia; Mastragostino, Marina

doi:10.1016/j.jpowsour.2014.12.099

Cited by 29 publications

(24 citation statements)

References 18 publications

(20 reference statements)

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“…According to other studies [4,39,40], the plateau around 4.0 V reflects the redox reaction of the Mn 3+ /Mn 4+ couple. However, the 4.0 V plateaus of our materials are too tiny to be distinguished, indicating that a small amount of Mn 3+ exists in the samples [34].…”

Section: Resultsmentioning

confidence: 65%

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: 65%

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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“…[3][4][5] The coating of surface protective layers on pristine LMNO particles has been extensively studied in literature. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] These layers provide a shield from the HF, and prevent rapid capacity fade, leading to improved cycling performance and capacity retention. Of the different surface coating techniques, atomic layer deposition (ALD) has inherent advantages that provide conformal, pin-hole free, size-tunable ultrathin films 21 and, thus, provide high capacity retention and a long life cycle.…”

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confidence: 99%

Ultrathin Conductive CeO₂Coating for Significant Improvement in Electrochemical Performance of LiMn_1.5Ni_0.5O₄Cathode Materials

Patel

Palaparty

Liu

2016

J. Electrochem. Soc.

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LiMn 1.5 Ni 0.5 O 4 (LMNO) has a huge potential for use as a cathode material in electric vehicular applications. However, it could face discharge capacity degradation with cycling at elevated temperatures due to attacks by hydrofluoric acid (HF) from the electrolyte, which could cause cationic dissolution. To overcome this barrier, we coated 3-5 micron sized LMNO particles with a ∼3 nm optimally thick and conductive CeO 2 film prepared by atomic layer deposition (ALD). This provided optimal thickness for mass transfer resistance, species protection, and mitigation of cationic dissolution at elevated temperatures. After 1,000 cycles of chargedischarge between 3.5 V-5 V (vs. Li + /Li) at 55 • C, the optimally coated sample, 50Ce (50 cycles of CeO 2 ALD coated) had a capacity retention of ∼97.4%, when tested at a 1C rate, and a capacity retention of ∼83% at a 2C rate. This was compared to uncoated LMNO particles that had a capacity retention of only ∼82.7% at a 1C rate, and a capacity retention of ∼40.8% at a 2C rate. Lithium ion batteries have emerged as potential candidates for replacement of Ni-Cd batteries in electric vehicles because of their high intrinsic energy densities combined with their ease of portability. This potential creates a need for the development of new or modified cathode and anode materials that possess high energy density, long cycle life, excellent capacity retention, and a large voltage window for operation. For electric vehicles, in particular, the upper voltage cutoff window on the cathode side should be ∼5 V vs. Li + /Li. Lithium manganese nickel oxide LiMn 1.5 Ni 0.5 O 4 (LMNO) has emerged in the research community as a potential cathode material for use in electric vehicles due to its large theoretical capacity of ∼148 mAhg −1 , a high working voltage of ∼4.7 V vs. Li + /Li, and a high energy density. 1,2However, LMNO suffers from high capacity fade during performance at elevated temperatures because Mn dissolves due to generation of hydrofluoric acid (HF) in the electrolyte. 3-5The coating of surface protective layers on pristine LMNO particles has been extensively studied in literature. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] These layers provide a shield from the HF, and prevent rapid capacity fade, leading to improved cycling performance and capacity retention. Of the different surface coating techniques, atomic layer deposition (ALD) has inherent advantages that provide conformal, pin-hole free, size-tunable ultrathin films 21 and, thus, provide high capacity retention and a long life cycle. The ALD process involves a sequence of self-limiting reactions that result in a coating of one monolayer at a time. This enables size tunability at the sub-nanometer level and promotes conformity in the films. Materials like Al 2 O 3 , 17 MgF 2 , 22 TiO 2 , 18 and LiAlO 2 10 have been studied as coating materials prepared by ALD on LMNO. Even though, these materials have provided effective mitigation of cationic dissolution, the ionic conductivity of such protective layers ...

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“…1 LiN 0.5 Mn 1.5 O 4 (LNMO)/graphene composites have recently been developed [20][21][22] by suspending mildly oxidized graphene and LNMO in ethanol to obtain graphene-wrapped LNMO. Graphene acts as a protective layer that minimizes the Mn 2+ dissolution in electrolyte and limits the unwanted parasitic electrode reactions, which affect both capacity and coulombic efficiency.…”

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confidence: 99%

“…Graphene oxide (GO) is usually added to the precursors of the cathode materials so that the synthesis of the latter and GO reduction occur simultaneously during pyrolysis under reducing atmosphere. 1 LiN 0.5 Mn 1.5 O 4 (LNMO)/graphene composites have recently been developed [20][21][22] by suspending mildly oxidized graphene and LNMO in ethanol to obtain graphene-wrapped LNMO. Graphene acts as a protective layer that minimizes the Mn 2+ dissolution in electrolyte and limits the unwanted parasitic electrode reactions, which affect both capacity and coulombic efficiency.…”

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confidence: 99%

Reduced Graphene Oxide in Cathode Formulations Based on LiNi_0.5Mn_1.5O₄

Arbizzani

Col

Giorgio

et al. 2015

J. Electrochem. Soc.

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We investigated the electrochemical properties of composite cathodes obtained by mixing LiNi 0.5 Mn 1.5 O 4 (LNMO), reduced graphene oxide (RGO) and carbon black (C65). Electrochemical electrode characterization was carried out in ethylene carbonate: dimethyl carbonate and 1 M LiPF 6 by galvanostatic charge/discharge cycles up to 4.8 V vs. Li + /Li and impedance spectroscopy. We demonstrate that RGO improves the electrode/electrolyte interface stability at high potentials and, consequently, the cycling stability of LNMO cathodes in the presence of C65 with 92% capacity retention after 100 cycles at 1 C. The reciprocal effect of RGO and C65 is also beneficial for rate capability, which retained a specific capacity of 75 mAh g −1 at 10 C. The electric contact between particles is promoted by C65 s conductive percolating network; RGO enhances the electrical conductivity of the composite electrode and hinders undesirable reactions between LNMO and the electrolyte. Despite RGO's lower electronic resistivity with respect to C65, the addition of RGO alone to LNMO is not sufficient to assure good performance. The mixing procedure without C65 promotes the agglomeration of graphene nanosheets rather than their distribution among LNMO particles and aggregates, limiting the electron and Li + transport in the cathode material. The appealing properties of graphene have attracted great attention in several research fields. Its superior electric conductivity, chemical stability and high flexibility make it of great interest as electrode material and additive in energy storage and conversion systems. [13][14][15][16][17][18][19] For example, the addition of graphene to lithium metal phosphates, which display low electrical conductivity (near 10 −9 -10 −7 S cm −1 ), boosts electronic conductivity, enhances microstructure via the formation of a three-dimensional network that shortens the lithium ion diffusion distance, and improves morphology by hindering grain growth.Directly adding graphene during conventional or non-conventional syntheses is often pursued. Graphene oxide (GO) is usually added to the precursors of the cathode materials so that the synthesis of the latter and GO reduction occur simultaneously during pyrolysis under reducing atmosphere.1 LiN 0.5 Mn 1.5 O 4 (LNMO)/graphene composites have recently been developed [20][21][22] by suspending mildly oxidized graphene and LNMO in ethanol to obtain graphene-wrapped LNMO. Graphene acts as a protective layer that minimizes the Mn 2+ dissolution in electrolyte and limits the unwanted parasitic electrode reactions, which affect both capacity and coulombic efficiency.Large-size battery production needs bulk syntheses of cathode materials and viable, inexpensive methods of preparing the composite electrode with graphene. Simple mixing of cathode composite components that include graphene might be a preferable, albeit nonoptimal, procedure. We thus investigated several mixing procedures for LNMO-based composites with reduced graphene oxide (RGO) and carbon black. The results o...

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Electrochemical performance of LiNi0.5Mn1.5O4 composite electrodes featuring carbons and reduced graphene oxide

Cited by 29 publications

References 18 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

Ultrathin Conductive CeO₂Coating for Significant Improvement in Electrochemical Performance of LiMn_1.5Ni_0.5O₄Cathode Materials

Reduced Graphene Oxide in Cathode Formulations Based on LiNi_0.5Mn_1.5O₄

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Electrochemical performance of LiNi0.5Mn1.5O4 composite electrodes featuring carbons and reduced graphene oxide

Cited by 29 publications

References 18 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

Ultrathin Conductive CeO2Coating for Significant Improvement in Electrochemical Performance of LiMn1.5Ni0.5O4Cathode Materials

Reduced Graphene Oxide in Cathode Formulations Based on LiNi0.5Mn1.5O4

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Ultrathin Conductive CeO₂Coating for Significant Improvement in Electrochemical Performance of LiMn_1.5Ni_0.5O₄Cathode Materials

Reduced Graphene Oxide in Cathode Formulations Based on LiNi_0.5Mn_1.5O₄