Effect of Bi oxide surface treatment on 5V spinel LiNi0.5Mn1.5−xTixO4

Noguchi, Takehiro; Yamazaki, Ikiko; Numata, Tatsuji; Shirakata, Masato

doi:10.1016/j.jpowsour.2007.06.139

Cited by 82 publications

(39 citation statements)

References 20 publications

(16 reference statements)

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“…6 However, LMNO reveals poor electrochemical performance. The capacity fading phenomenon is considered to be due to the large lattice strain upon cycling since it involves the formation of three cubic phases with a large lattice parameter difference during the charge/discharge process in addition to the corrosion reaction between the cathode surface and the electrolyte at the high operating voltage of ~5 V. [7][8][9] Some of the partial substitution of Mn and Ni in LMNO by other elements such as Mg, Cr, Fe, Co, Mo, W, and Tb has been pursued to enhance the electrochemical performance.…”

Section: +/4+mentioning

confidence: 99%

“…8,9 The surface modification including conductive agents like carbon and aluminum has been successfully applied to the cathodes, where the formation of conductive coating layers consisting of nanostructured carbon materials leads to improved electronic conductivity, cyclability, and rate capability. [15][16][17] Based on these approaches, graphene has been considered as an effective conductive coating material due to its outstanding physical properties including high specific surface area, high electronic conductivity, and excellent structural stability.…”

Section: -14mentioning

confidence: 99%

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Synthesis and Electrochemical Performance of Reduced Graphene Oxide/AlPO₄-coated LiMn_1.5Ni_0.5O₄for Lithium-ion Batteries

Hur¹,

Kim²

2014

Bulletin of the Korean Chemical Society

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The reduced graphene oxide(rGO)/aluminum phosphate(AlPO 4 )-coated LiMn 1.5 Ni 0.5 O 4 (LMNO) cathode material has been developed by hydroxide precursor method for LMNO and by a facile solution based process for the coating with GO/AlPO 4 on the surface of LMNO, followed by annealing process. The amount of AlPO 4 has been varied from 0.5 wt % to 1.0 wt %, while the amount of rGO is maintained at 1.0 wt %. The samples have been characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. The rGO/AlPO 4 -coated LMNO electrodes exhibit better cyclic performance compared to that of pristine LMNO electrode. Specifically, rGO(1%)/AlPO 4 (0.5%)-and rGO(1%)/AlPO 4 (1%)-coated electrodes deliver a discharge capacity of, respectively, 123 mAh g −1 and 122 mAh g −1 at C/6 rate, with a capacity retention of, respectively, 96% and 98% at 100 cycles. Furthermore, the surface-modified LMNO electrodes demonstrate higher-rate capability. The rGO(1%)/AlPO 4 (0.5%)-coated LMNO electrode shows the highest rate performance demonstrating a capacity retention of 91% at 10 C rate. The enhanced electrochemical performance can be attributed to (1) the suppression of the direct contact of electrode surface with the electrolyte, resulting in side reactions with the electrolyte due to the high cut-off voltage, and (2) smaller surface resistance and charge transfer resistance, which is confirmed by total polarization resistance and electrochemical impedance spectroscopy.

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Section: +/4+mentioning

confidence: 99%

Section: -14mentioning

confidence: 99%

Synthesis and Electrochemical Performance of Reduced Graphene Oxide/AlPO₄-coated LiMn_1.5Ni_0.5O₄for Lithium-ion Batteries

Hur¹,

Kim²

2014

Bulletin of the Korean Chemical Society

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“…3 There have been several methods developed to inhibit the detrimental reactions of the electrolyte with LNMS including surface modification with various inorganic oxides including Al 2 O 3 , 4 ZnO, 4,5 and Bi 2 O 3 . 4,6 The surface-modified cathodes have superior cyclability compared to the uncoated cathode, suggesting that the coatings form a stable passivation layer or a solid electrolyte interface ͑SEI͒ on the cathode. An alternative approach using sacrificial electrolyte additives for in situ formation of a cathode SEI has also been reported to improve cycling to 4.9 V vs LRE.…”

mentioning

confidence: 99%

Electrolyte Reactions with the Surface of High Voltage LiNi[sub 0.5]Mn[sub 1.5]O[sub 4] Cathodes for Lithium-Ion Batteries

Yang

Ravdel²,

Lucht

2010

Electrochem. Solid-State Lett.

487

413

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There is significant interest in the development of higher energy lithium-ion batteries for electric vehicles, hybrid electric vehicles, and aerospace applications. One method of improving the energy density of lithium-ion batteries is to increase the operating voltage of the cells by increasing the working potentials of positive electrode employing, for example, lithium nickel manganese spinel ͓LiNi 0.5 Mn 1.5 O 4 ͑LNMS͔͒ as the active material.1 However, cycling of lithium-ion cells to high voltages ͓ϳ5.0 V vs lithium reference electrode ͑LRE͔͒ proceeds with relatively low ͑99% and less͒ coulombic efficiency.2 Among the primary contributors to the poor cycling efficiency are the electrochemical oxidation reactions of the electrolytes at the high positive potentials of the positive electrode. 4,6 The surface-modified cathodes have superior cyclability compared to the uncoated cathode, suggesting that the coatings form a stable passivation layer or a solid electrolyte interface ͑SEI͒ on the cathode. An alternative approach using sacrificial electrolyte additives for in situ formation of a cathode SEI has also been reported to improve cycling to 4.9 V vs LRE. 7 There have been several investigations of the structure of cathode surface films formed under standard cycling ͑Ͻ4.5 V vs LRE͒ and aging conditions. 8-10 However, there have not been any detailed investigations of the cathode surface film structure as a function of electrode potential, especially at high voltage ͑Ͼ4.5 V vs LRE͒. Problems associated with reactions of the electrolyte on the surface of high voltage cathode materials have been reported to limit the application of these interesting materials.2,4 We present here an investigation of the voltagedependent electrochemical reactions in 1 M LiPF 6 in ethylene carbonate ͑EC͒/diethyl carbonate ͑DEC͒/dimethyl carbonate ͑DMC͒ ͑1/ 1/1 vol͒ on an LNMS-based electrode and the characterization of the surface species by XPS and Fourier transform infrared spectroscopy with attenuated total reflectance ͑FTIR-ATR͒. Our results suggest that poly͑ethylenecarbonate͒ ͑PEC͒ derived from the oxidative polymerization of EC is the primary component of the cathode SEI upon high voltage cycling. ExperimentalCoin-type cells with mixed metal oxide-based positive and lithium-metal negative electrodes and filled with 1 M solution of LiPF 6 in EC/DMC/DEC ͑1/1/1 vol͒ were used in the experiments. Two tests were undertaken. In the first one, a lithium-free material, nickel manganese mixed oxide ͑Ni 0.5 Mn 1.5 O 3 ͒, as the positive electrode mimicking the LNMS material was employed in two-electrode half-cells. The binder in the first set was based on poly͑vinylidene flouride͒ ͑PVDF, Kureha 1910͒. In the second experiment, the cathode was based on an LMNS adhered by a fluorine-free binder, ethylene propylene diene monomer ͑EPDM, Vistalon 2504͒ rubber, dissolved in toluene. Both experiments used two-electrode half-cells with aluminum current collectors. The electrodes contained 81% of active material and increased fraction ͑8%͒ of ...

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“…[ 17,18 ] Unlike other elemental dopants, the Ti-substitution improved cycle lives of full cells using various anode materials including amorphous carbon, graphite, and Li 4 Ti 5 O 12 (LTO). [18][19][20] High Coulombic effi ciency (CE) and low self-discharge rates of the LiNi 0.5 Mn 1.5− x Ti x O 4 cathode compared with the Ti-free LNMO show that the Ti-substitution mitigates electrolyte oxidation and/or transition metal dissolution at the cathode/electrolyte interface. [ 18 ] However, the improvement mechanism(s) in the LiNi 0.5 Mn 1.5− x Ti x O 4 full cells has not been identifi ed.…”

Section: Introductionmentioning

confidence: 99%

In Situ Formation of a Cathode–Electrolyte Interface with Enhanced Stability by Titanium Substitution for High Voltage Spinel Lithium‐Ion Batteries

Kim

Pieczonka

Lü

et al. 2015

Adv Materials Inter

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Although LiNi0.5Mn1.5O4 (LNMO) high‐voltage spinel is a promising candidate for a next generation cathode material, LNMO/graphite full cells experience severe capacity fading caused by degradation reactions at electrode/electrolyte interfaces and consequent active Li+ loss in the cells. In this study, it is first reported that in situ formation of a Ti–O enriched cathode/electrolyte interfacial (CEI) layer on a Ti‐substituted LiNi0.5Mn1.2Ti0.3O4 (LNMTO) spinel cathode effectively mitigates electrolyte oxidation and transition metal dissolution, which improves the Coulombic efficiency and cycle life of LNMTO/graphite full cells. The Ti–O enriched CEI layer is produced in situ during an initial cycling of LNMTO as a result of selective Mn and Ni dissolution at its surface, as evidenced by various surface characterizations using X‐ray photoelectron spectroscopy, transmission electron microscopy, time‐of‐flight secondary ion mass spectrometry, Raman spectroscopy, and synchrotron‐based soft X‐ray absorption spectroscopy. The Ti–O enriched CEI has an advantage over traditional LNMO powder coatings, namely the formation of conformal CEI without compromising electronic conduction pathways between cathode particles.

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Effect of Bi oxide surface treatment on 5V spinel LiNi0.5Mn1.5−xTixO4

Cited by 82 publications

References 20 publications

Synthesis and Electrochemical Performance of Reduced Graphene Oxide/AlPO₄-coated LiMn_1.5Ni_0.5O₄for Lithium-ion Batteries

Synthesis and Electrochemical Performance of Reduced Graphene Oxide/AlPO₄-coated LiMn_1.5Ni_0.5O₄for Lithium-ion Batteries

Electrolyte Reactions with the Surface of High Voltage LiNi[sub 0.5]Mn[sub 1.5]O[sub 4] Cathodes for Lithium-Ion Batteries

In Situ Formation of a Cathode–Electrolyte Interface with Enhanced Stability by Titanium Substitution for High Voltage Spinel Lithium‐Ion Batteries

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Effect of Bi oxide surface treatment on 5V spinel LiNi0.5Mn1.5−xTixO4

Cited by 82 publications

References 20 publications

Synthesis and Electrochemical Performance of Reduced Graphene Oxide/AlPO4-coated LiMn1.5Ni0.5O4for Lithium-ion Batteries

Synthesis and Electrochemical Performance of Reduced Graphene Oxide/AlPO4-coated LiMn1.5Ni0.5O4for Lithium-ion Batteries

Electrolyte Reactions with the Surface of High Voltage LiNi[sub 0.5]Mn[sub 1.5]O[sub 4] Cathodes for Lithium-Ion Batteries

In Situ Formation of a Cathode–Electrolyte Interface with Enhanced Stability by Titanium Substitution for High Voltage Spinel Lithium‐Ion Batteries

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Synthesis and Electrochemical Performance of Reduced Graphene Oxide/AlPO₄-coated LiMn_1.5Ni_0.5O₄for Lithium-ion Batteries

Synthesis and Electrochemical Performance of Reduced Graphene Oxide/AlPO₄-coated LiMn_1.5Ni_0.5O₄for Lithium-ion Batteries