Improved Electrochemical Performance and Thermal Stability of Li-excess Li1.18Co0.15Ni0.15Mn0.52O2 Cathode Material by Li3PO4 Surface Coating

Bian, Xiaofei; Fu, Qiang; Bie, Xiaofei; Yang, Peilei; Qiu, Hailong; Pang, Qiang; Chen, Gang; Du, Fei; Wei, Yingjin

doi:10.1016/j.electacta.2015.06.085

Cited by 112 publications

(70 citation statements)

References 39 publications

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“…B 1 s peak can be observed obviously at 191 eV in the 2‐LBP@LNMO sample, which is consistent with the B−O bond in FTIR spectra and suggests B existing in a depth of several nanometers on the surface . The P 2p signals was also detected in the coated sample around the binding energy 133 eV, which is in good agreement with the previous report on P−O bond in the tetrahedral [PO 4 ] 3− groups . The binding energy of Mn 2p 3/2 is located at 642 eV, in accordance with the Mn 4+ oxidation state in Li‐rich layered oxides.…”

Section: Resultssupporting

confidence: 90%

“…Bian et al. reported a Li 3 PO 4 protective layer to improve the rate capability and long‐term cycling stability of Li 1.18 Co 0.15 Ni 0.15 Mn 0.52 O 2 electrode . However, in order to generate the conductive layers, an additional amount of Li + source is introduced in the coating process, which may lead to the formation of excessive Li 2 CO 3 impurity on the surface and a poor processability of the modified materials.…”

Section: Introductionmentioning

confidence: 99%

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Improved Rate Capability of Li‐Rich Cathode Materials by Building a Li⁺‐Conductive Li_xBPO_4+x/2 Nanolayer from Residual Li₂CO₃ on the Surface

Yang

Chen

et al. 2017

ChemElectroChem

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Lithium-and manganese-rich layered oxides face great challenges for practical applications, including gradual voltage decay upon normal charge/discharge cycling and the relatively low volumetric energy density. This series of materials generally suffer from a great reduction in reversible capacity with an increase of the current density and the loading density of the electrode, which can be attributed to the low Li + conductivity of the material, as previously reported. Herein, BPO 4 is proposed to encapsulate Li 1.16 (Ni 0.25 Mn 0.75 ) 0.84 O 2 (LNMO) particles and is expected to form a Li-doped Li x BPO 4 + x/2 (LBP) layer as a lithiumion conductor on the particle surface to facilitate the transportation of Li + across the solidÀliquid interface. The results confirm that the LBP layer was formed, providing a lithium-ion diffusion path and suppressing the undesired interfacial reactions. A LNMO sample coated with 1.6 mol% LBP (LBP@LNMO) demonstrated excellent rate capability, retaining 90.2, 80.2, 61.2, and 43.5 % at 1, 2, 5, and 10 C rates of the capacity at the 0.5 C rate. Moreover, the modified material is clearly relieved from voltage fading and offers improved cycling stability at 55 8C, which mainly contributes to a decrease in the polarization and an increase in the interfacial stability under the protection of the LBP layer. It implies that the dual functional coating is an effective route to promote the lithium-transport kinetics.[a] L.

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Section: Resultssupporting

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Improved Rate Capability of Li‐Rich Cathode Materials by Building a Li⁺‐Conductive Li_xBPO_4+x/2 Nanolayer from Residual Li₂CO₃ on the Surface

Yang

Chen

et al. 2017

ChemElectroChem

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“…Likewise, oxygen non-stoichiometry also plays an important role in influencing the electrochemical performance of LMR cathode materials containing different amounts of Li 2 MnO 3 . Fast quenching of the LMR materials (in air, water, or liquid nitrogen) from high temperature (typically 900°C) has been frequently used to preserve the oxygen non-stoichiometry in order to achieve better electrochemical performance of LMR materials [95][96][97][98][99]. (Fig.…”

Section: Oxygen Non-stoichiometry In Lmr Layered-structure Cathodesmentioning

confidence: 99%

The roles of oxygen non-stoichiometry on the electrochemical properties of oxide-based cathode materials

2016

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Cathode materials with both high energy density and high power capability are in great demand to improve the performance of lithium ion batteries and expand the driving range of electric vehicles. Of particular interest are transition metal oxide-based cathodes. However, electrochemical performance of these cathode materials is very sensitive to the synthetic conditions and, particularly, the oxygen non-stoichiometry that is induced during high temperature synthesis and post-treatment. This review highlights the critical roles of oxygen nonstoichiometry in high-energy-density cathode materials including high voltage spinel LiNi 0.5 Mn 1.5 O 4 , Ni-rich layered LiNi x Mn y Co z O 2 (NMC, x > 0.5), and the Li-rich, Mn-rich layered cathode, with the aim to provide a fundamental understanding on the effects of the (J.-G. Zhang).Abbreviations: ALMO annealed Li 2 MnO 3 EELS electron energy loss spectroscopy EV electric vehicle LIB lithium ion battery LMR Li-rich Mn-rich MLMO quenched Li 2 MnO 3 milled with Super P NMC LiNi x Mn y Co z O 2 QLMO quenched Li 2 MnO 3 TG thermogravimetric TM transition metal © 2016. This manuscript version is made available under the Elsevier user license http://www.elsevier.com/open-access/userlicense/1.0/oxygen non-stoichiometry governing the crystalline structure, electrochemical performance, and thermal stability of different cathode materials. This review also offers perspectives and directions on how to best utilize oxygen non-stoichiometry in the future development of highenergy-density cathode materials for lithium ion batteries. KeywordsOxygen non-stoichiometry; Cathode materials; Ni-rich material; High voltage spinel; Li-rich Mn-rich; Lithium ion battery. Highlights Oxygen non-stoichiometry, which is sensitive to the synthesis conditions, plays a critical role in manipulating the material crystal structure. Oxygen non-stoichiometry fundamentally affects the reaction pathway, electrochemical performances and thermal stability of cathode materials. The effects of oxygen non-stoichiometry should be carefully considered in the future development of high-energy-density cathode materials for lithium-ion batteries.

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“…Most of the reported surface modifications are performed under solution-based reactions. [6][7][8] For example, Bian et al used LiOH and NH 4 H 2 PO 4 to coat Lithium-excess with Li 3 PO 4 .…”

mentioning

confidence: 99%

Communication—Enhancing the Electrochemical Performance of Lithium-Excess Layered Oxide Li_1.13Ni_0.3Mn_0.57O₂ via a Facile Nanoscale Surface Modification

Liu

Huang

Qian

et al. 2016

J. Electrochem. Soc.

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In this work, a facile surface modification with nanoscale equilibrium Li 3 PO 4 -based surface amorphous films (SAFs) has been applied to Lithium-excess layered oxide Li 1.13 Ni 0.3 Mn 0.57 O 2 , which significantly improves the first cycle coulombic efficiency, rate capability, and cycling stability. The nanoscale surface modification can be easily achieved by ballmilling and isothermal annealing. The optimized surface modified Li 1.13 Ni 0.3 Mn 0.57 O 2 is capable of maintaining a high capacity of 201 mAh g −1 after 60 cycles at 55 • C testing with a rate of 1 C. This work provides a facile and scalable surface modification method to improve electrochemical performance of cathode materials for lithium ion batteries. The Lithium-excess layered oxides benefit from an extraordinary high reversible capacity (>280 mAh g −1 ) and is one of the most promising cathode materials for plug-in electric vehicle application. [1][2][3] However, this high-energy-density material suffers from large irreversible capacity in its first electrochemical cycle when it is charged to high voltages, namely more than 4.6 V. In addition, its rate capability is yet unsatisfactory for high power application. Moreover, the gradual voltage and capacity degradation upon electrochemical cycling, especially at elevated temperature when side reactions related to the interactions with the electrolyte occur more prevalently, represent the most serious technical challenge for this material. 4,5 In the past few years, significant amount of surface modification works have been carried out to protect the surfaces of the Li-excess. Most of the reported surface modifications are performed under solution-based reactions.6-8 For example, Bian et al. used LiOH and NH 4 H 2 PO 4 to coat Lithium-excess with Li 3 PO 4 .7 However, the solution based surface modification adds an additional layer of complexity for preparation of Lithium-excess, which will definitely raise the cost of production. Although Konishi coated high voltage spinel LiNi 0.5 Mn 1.5 O 4 with uniform Li 3 PO 4 via pulsed laser deposition (PLD), this technique requires special equipment, which is difficult to realize for large scale production. 9In this work, we modify the surface of Lithium-excess layered oxide Li 1.13 Ni 0.3 Mn 0.57 O 2 via simple mixing and calcination to form Li 3 PO 4 -enriched and nanometer-thick surface amorphous films (SAFs). 10 Our results indicate that the optimized material shows remarkably improved performance. ExperimentalThe synthesis of the Li-excess is described in our previous publications. 3,6 The procedure for preparing Li 3 PO 4 surface modified Li 1.13 Ni 0.3 Mn 0.57 O 2 (LPLNMO) was adapted from work by Huang et al.10 0.06 g Li 3 PO 4 (Alfa Aesar, 99.99%) and 3 g Li 1.13 Ni 0.3 Mn 0.57 O 2 were mixed using a planetary ball mill (PM 100, Retsch). The powder was calcinated at 500• C (LP500), 600• C (LP600), and 700• C (LP700), respectively, for 5 h in air. Electrochemical test, XRD, SEM and HRTEM characterization are described with details in our previous...

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Improved Electrochemical Performance and Thermal Stability of Li-excess Li1.18Co0.15Ni0.15Mn0.52O2 Cathode Material by Li3PO4 Surface Coating

Cited by 112 publications

References 39 publications

Improved Rate Capability of Li‐Rich Cathode Materials by Building a Li⁺‐Conductive Li_xBPO_4+x/2 Nanolayer from Residual Li₂CO₃ on the Surface

Improved Rate Capability of Li‐Rich Cathode Materials by Building a Li⁺‐Conductive Li_xBPO_4+x/2 Nanolayer from Residual Li₂CO₃ on the Surface

The roles of oxygen non-stoichiometry on the electrochemical properties of oxide-based cathode materials

Communication—Enhancing the Electrochemical Performance of Lithium-Excess Layered Oxide Li_1.13Ni_0.3Mn_0.57O₂ via a Facile Nanoscale Surface Modification

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Improved Electrochemical Performance and Thermal Stability of Li-excess Li1.18Co0.15Ni0.15Mn0.52O2 Cathode Material by Li3PO4 Surface Coating

Cited by 112 publications

References 39 publications

Improved Rate Capability of Li‐Rich Cathode Materials by Building a Li+‐Conductive LixBPO4+x/2 Nanolayer from Residual Li2CO3 on the Surface

Improved Rate Capability of Li‐Rich Cathode Materials by Building a Li+‐Conductive LixBPO4+x/2 Nanolayer from Residual Li2CO3 on the Surface

The roles of oxygen non-stoichiometry on the electrochemical properties of oxide-based cathode materials

Communication—Enhancing the Electrochemical Performance of Lithium-Excess Layered Oxide Li1.13Ni0.3Mn0.57O2 via a Facile Nanoscale Surface Modification

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Improved Rate Capability of Li‐Rich Cathode Materials by Building a Li⁺‐Conductive Li_xBPO_4+x/2 Nanolayer from Residual Li₂CO₃ on the Surface

Improved Rate Capability of Li‐Rich Cathode Materials by Building a Li⁺‐Conductive Li_xBPO_4+x/2 Nanolayer from Residual Li₂CO₃ on the Surface

Communication—Enhancing the Electrochemical Performance of Lithium-Excess Layered Oxide Li_1.13Ni_0.3Mn_0.57O₂ via a Facile Nanoscale Surface Modification