Enhanced electrochemical performance of Li-rich cathode Li1.2Ni0.2Mn0.6O2 by surface modification with WO3 for lithium ion batteries

Mu, Kunchang; Cao, Yanbing; Hu, Guorong; Du, Ke; Yang, Hao; Gan, Zhanggen; Peng, Zhongdong

doi:10.1016/j.electacta.2018.04.027

Cited by 91 publications

(45 citation statements)

References 40 publications

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“…[45] The soft X-ray absorption (sXAS) analysis in Figure 2g indicates that the Mn valence at the particle surface was still +4.0 after ASR, which corroborates that the amount of [VÖ] in the shell was negligible after ASR, otherwise there must be Mn 3+ ions if the spinel shell contains appreciable amount of [VÖ]. [46,47] The ASR at high temperature also annealed out most of the prolific grain boundaries and/or exposed surfaces that could be generated in foreign coatings, [48][49][50] which are preferential locations for GOM and stress-corrosion cracking (SCC) in electrolyte, making the spinel shell crystal robust to sufficiently prevent GOM and stabilize the cycling performance.…”

Section: Artificial Surface Prereconstruction For LI 12 Mn 06 Ni 0mentioning

confidence: 60%

Stabilized Co‐Free Li‐Rich Oxide Cathode Particles with An Artificial Surface Prereconstruction

Zhi

Gao

Waluyo

et al. 2020

Advanced Energy Materials

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Li‐rich metal oxide (LXMO) cathodes have attracted intense interest for rechargeable batteries because of their high capacity above 250 mAh g−1. However, the side effects of hybrid anion and cation redox (HACR) reactions, such as oxygen release and phase collapse that result from global oxygen migration (GOM), have prohibited the commercialization of LXMO. GOM not only destabilizes the oxygen sublattice in cycling, aggravating the well‐known voltage fading, but also intensifies electrolyte decomposition and Mn dissolution, causing severe full‐cell performance degradation. Herein, an artificial surface prereconstruction (ASR) for Li1.2Mn0.6Ni0.2O2 particles with a molten‐molybdate leaching is conducted, which creates a crystal‐dense anion‐redox‐free LiMn1.5Ni0.5O4 shell that completely encloses the LXMO lattice (ASR‐LXMO). Differential electrochemical mass spectroscopy and soft X‐ray absorption spectroscopy analyses demonstrate that GOM is shut down in cycling, which not only stabilizes HACR in ASR‐LXMO, but also mitigates the electrolyte decomposition and Mn dissolution. ASR‐LXMO displays greatly stabilized cycling performance as it retains 237.4 mAh g−1 with an average discharge voltage of 3.30 V after 200 cycles. More crucially, while the pristine LXMO cycling cannot survive 90 cycles in a pouch full‐cell matched with a commercial graphite anode and lean (2 g A−1 h−1) electrolyte, ASR‐LXMO shows high capacity retention of 76% after 125 cycles in full‐cell cycling.

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Section: Artificial Surface Prereconstruction For LI 12 Mn 06 Ni 0mentioning

confidence: 60%

Stabilized Co‐Free Li‐Rich Oxide Cathode Particles with An Artificial Surface Prereconstruction

Zhi

Gao

Waluyo

et al. 2020

Advanced Energy Materials

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“…Such coating processes can involve chemical reactions between precursors in the liquid phase and the active mass, which form the final desirable coating. As examples, the following materials were used as coating layers to protect cathode materials from side reactions through deposition from the liquid phase: oxides (e.g., MgO, [87] Al 2 O 3 , [88] MnO 2 , [48] Pr 6 O 11 , [89] WO 3 , [90] CeO 2 , [91] MoO 3 [92] ), fluorides (e.g., CaF 2 , [93] LiF/FeF 3 , [94] CoF 2 , [95] ZrF 4 , [96] YF 3 , [97] AlF 3 [98] ), phosphates (e.g., AlPO 4 , [99] FePO 4 /Li 3 PO 4 , [100] SmPO 4 [101] ), lithium ion conductive oxides (e.g., Li 4 Ti 5 O 12 , [102] Li 2 ZrO 3 , [103] Li 2 WO 3 , [104] Li 2 MnO 3 , [105] Li-Ni-Co-O [106] ), conducting polymers (e.g., PEDOT:PSS [107] and LiPPA/PPy [85a] ) and carbon. [108] Indeed, Kobayashi et al reported that the hightemperature cycling performance of LMLO cathodes improved due to Al 2 O 3 coating and precycling.…”

Section: Deposition From the Liquid Phasementioning

confidence: 99%

“…[108] Indeed, Kobayashi et al reported that the hightemperature cycling performance of LMLO cathodes improved due to Al 2 O 3 coating and precycling. [88] As shown in Figure 4a, Mu et al prepared coating by WO 3 using an ammonia solution, [90] which increased the first cycle coulombic efficiency from 72% to 92.5% and demonstrated a protective effect against HF. Another interesting example is coating of LMLO by a protective layer of Li 2 MnO 3 from anhydrous ethanolic solution containing lithium and manganese acetates.…”

Section: Deposition From the Liquid Phasementioning

confidence: 99%

Surface Modification of Li‐Rich Mn‐Based Layered Oxide Cathodes: Challenges, Materials, Methods, and Characterization

Lei

et al. 2020

Advanced Energy Materials

135

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high energy and power density, long cycle life, low cost, and environmental benignity. [3] Due to the high capacity of the currently used graphite anode −372 mAh g-1 , [1b,4] commercial cathodes have become the bottleneck for improving the energy density. [5] In addition, cathode materials take up about 40% of the total material cost of typical LIB cells. It is therefore crucial to develop cathode materials with high energy density and low cost, while maintaining superior safety features. [6] Driven by the wide deployment of electric vehicles in recent years, the demand for safer cathode materials with higher capacity and lower cost has become imperative. [2b] The specific capacity depends on the inherent physical properties of the cathode materials. Commercial materials such as LiCoO 2 , Li(Ni x Mn y Co z)O 2 , Li(Ni x Co y Al z)O 2 , LiMn 2 O 4 and LiFePO 4 all possess discharge capacities below 200 mAh g-1. [7] Ni-rich NCM, NCA, and Li-rich oxides are all prospective cathodes for high-energy LIBs as they can exhibit high specific discharge capacities above 200 mAh g-1. [6c] As compared with Ni-rich NCM and NCA, Li-rich Mn-based layered oxide (LMLO) cathode materials are cheaper and have higher specific capacity. They can deliver an initial specific discharge capacity that approaches 300 mAh g-1 , nearly doubling the capacity of commercially used cathodes and close to the limit for lithiated transition metal oxides. [8] Figure 1 lists the main development milestones of LMLO. In 1997 a novel material, LiCoO 2-Li 2 MnO 3 , was found by Numata et al., [9] a discovery that initiated intensive work on high energy density cathode materials. This group studied these materials intensively and demonstrated their cycling stability in the range of 3.0-4.3 V versus Li. [10] In 1999, Kalyani et al. reported that Li 2 MnO 3 can undergo electrochemical activation at potentials >4.5 V versus Li. [11] Dahn et al. described the charge compensation mechanism of LMLO, [12] and these cathodes were shown to provide high capacity at high operational voltage (>4.5 V). [13] In 2004, Thackeray et al. explored xLi 2 M′O 3-(1-x)LiMn 0.5 Ni 0.5 O 2 cathode materials with M′ = Zn, Ti, or Mn, concluding that Li 2 M′O 3 and LiMn 0.5 Ni 0.5 O 2 in these composite materials were integrated by short-range interactions. [14] The following Rechargeable lithium-ion batteries have become the dominant power sources for portable electronic devices, and are regarded as the battery technology of choice for electric vehicles and as potential candidates for grid-scale storage. Commercial lithium-ion batteries, after three decades of cell engineering, are approaching their energy density limits. Toward continually improving the energy density and reducing cost, Li-rich Mn-based layered oxide (LMLO) cathodes are receiving more and more attention due to their high discharge capacity and low cost. However, commercialization has been hampered by severe capacity and voltage decay, sluggish rate capability, and poor safety performance during charge/discharge cyc...

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“…To overcome these issues, various optimization techniques such as surface modification, doping of transition metals and morphology control have been widely reported [11,18,27]. Among them, the surface coating is widely accepted by the battery community for improving the performance of cathode materials for lithium-ion batteries [10,11].…”

Section: Introductionmentioning

confidence: 99%

Improved electrochemical performance of SiO2-coated Li-rich layered oxides-Li1.2Ni0.13Mn0.54Co0.13O2

Abraham

Nisar

Monawwar

et al. 2020

J Mater Sci: Mater Electron

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Lithium-rich layered oxides (LLOs) such as Li1.2Ni0.13Mn0.54Co0.13O2 are suitable cathode materials for future lithium-ion batteries (LIBs). Despite some salient advantages, like low cost, ease of fabrication, high capacity, and higher operating voltage, these materials suffer from low cyclic stability and poor capacity retention. Several different techniques have been proposed to address the limitations associated with LLOs. Herein, we report the surface modification of Li1.2Ni0.13Mn0.54Co0.13O2 by utilizing cheap and readily available silica (SiO2) to improve its electrochemical performance. Towards this direction, Li1.2Ni0.13Mn0.54Co0.13O2 was synthesized utilizing a sol–gel process and coated with SiO2 (SiO2 = 1.0 wt%, 1.5 wt%, and 2.0 wt%) employing dry ball milling technique. XRD, SEM, TEM, elemental mapping and XPS characterization techniques confirm the formation of phase pure materials and presence of SiO2 coating layer on the surface of Li1.2Ni0.13Mn0.54Co0.13O2 particles. The electrochemical measurements indicate that the SiO2-coated Li1.2Ni0.13Mn0.54Co0.13O2 materials show improved electrochemical performance in terms of capacity retention and cyclability when compared to the uncoated material. This improvement in electrochemical performance can be related to the prevention of electrolyte decomposition when in direct contact with the surface of charged Li1.2Ni0.13Mn0.54Co0.13O2 cathode material. The SiO2 coating thus prevents the unwanted side reactions between cathode material and the electrolyte. 1.0 wt% SiO2-coated Li1.2Ni0.13Mn0.54Co0.13O2shows the best electrochemical performance in terms of rate capability and capacity retention.

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Enhanced electrochemical performance of Li-rich cathode Li1.2Ni0.2Mn0.6O2 by surface modification with WO3 for lithium ion batteries

Cited by 91 publications

References 40 publications

Stabilized Co‐Free Li‐Rich Oxide Cathode Particles with An Artificial Surface Prereconstruction

Stabilized Co‐Free Li‐Rich Oxide Cathode Particles with An Artificial Surface Prereconstruction

Surface Modification of Li‐Rich Mn‐Based Layered Oxide Cathodes: Challenges, Materials, Methods, and Characterization

Improved electrochemical performance of SiO2-coated Li-rich layered oxides-Li1.2Ni0.13Mn0.54Co0.13O2

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