In situ Sr2+-doped spinel LiNi0.5Mn1.5O4 cathode material for Li-ion batteries with high electrochemical performance and its impact on morphology

Ji, Xiang; Dai, Xinyi; Wu, Fuzhong; Mai, Yi; Chen, Haijun; Gu, Yijing

doi:10.1016/j.ceramint.2021.08.093

Cited by 27 publications

(15 citation statements)

References 60 publications

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“…Up to now, common nonmetal elements (B, [55,56] S, [15] N, [57] F, [58] etc.) and the metal elements (Sr, [59] Al, [26] Ni, [60,61] etc.) have been widely studied.…”

Section: Element Dopingmentioning

confidence: 99%

Engineering Crystal Orientation of Cathode for Advanced Lithium‐Ion Batteries: A Minireview

Zhu

Zhou

Yang

et al. 2022

The Chemical Record

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Engineering crystal orientation has attracted widespread attention since it is related to the cyclability and rate performance of cathode materials for lithium‐ion batteries (LIBs). Regulating the crystal directional growth with optimal exposed crystal facets is an effective strategy to improve the performance of cathode materials, but still lacks sufficient attention in research field. Herein, we briefly introduce the characterization techniques and identification methods for crystal facets, then summarize and illuminate the major methods for regulating crystal orientation and their internal mechanism. Furthermore, the optimization strategies for layered‐, spinel‐, and olivine‐structure cathodes are discussed based on the characteristic of crystal structure, and the relationship between exposure of special crystal facets and lithium storage performance is deeply analyzed, which could guide the rational design of cathodes for LIBs.

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“…Up to now, common nonmetal elements (B, [55,56] S, [15] N, [57] F, [58] etc.) and the metal elements (Sr, [59] Al, [26] Ni, [60,61] etc.) have been widely studied.…”

Section: Element Dopingmentioning

confidence: 99%

Engineering Crystal Orientation of Cathode for Advanced Lithium‐Ion Batteries: A Minireview

Zhu

Zhou

Yang

et al. 2022

The Chemical Record

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“…One is the Fd 3̅ m disordered space group, in which Mn and Ni are stochastically assigned in 16d; the other is the P 4 3 32 ordered space group, where Mn and Ni dominate the 12d and 4a, respectively. , XRD cannot effectively distinguish between these two space groups because of the comparable scattering factors of Mn and Ni ions; thus, all samples were examined using FT-IR spectroscopy, as shown in Figure c. According to the relevant literature, the infrared absorption spectrum of the P 4 3 32 ordered space group has 8 absorption peaks, while the Fd 3̅m disordered space group has only five absorption peaks . The absorption peaks at approximately 623 and 558 cm –1 correspond to the stretching vibration of the Mn–O bond, while the absorption peaks around 587 and 502 cm –1 correspond to the vibration of the Ni–O bond .…”

Section: Resultsmentioning

confidence: 99%

“…The CeF 3 -coated LNMO cathode material was prepared via the liquid-phase method, and the preparation process is shown in Figure a. LNMO was synthesized in our previous work . Ce(NO 3 ) 3 ·6H 2 O (chemical reagent, 99%) and NH 4 F with a molar ratio of 1:3 were dissolved in deionized water, respectively, and then into a uniformly dispersed LNMO solution to obtain CeF 3 -modified (0.5, 1, 2 wt %) LNMO samples.…”

Section: Methodsmentioning

confidence: 99%

“…LNMO was synthesized in our previous work. 33 Ce(NO 3 ) 3 •6H 2 O (chemical reagent, 99%) and NH 4 F with a molar ratio of 1:3 were dissolved in deionized water, respectively, and then into a uniformly dispersed LNMO solution to obtain CeF 3modified (0.5, 1, 2 wt %) LNMO samples. The resulting solution was vigorously agitated and vaporized at 60 °C for 4 h and then desiccated in an oven at 100 °C for 12 h. Eventually, the prepared samples were annealed at 500 °C in argon for 4 h to form CeF 3 -LNMO (simply as LNMO, 0.5, 1, and 2 wt %-CF).…”

Section: ■ Introductionmentioning

confidence: 99%

“…According to the relevant literature, the infrared absorption spectrum of the P4 3 32 ordered space group has 8 absorption peaks, while the Fd3̅ m disordered space group has only five absorption peaks. 33 The absorption peaks at approximately 623 and 558 cm −1 correspond to the stretching vibration of the Mn−O bond, while the absorption peaks around 587 and 502 cm −1 correspond to the vibration of the Ni−O bond. 23 The results clearly illustrate that both the LNMO and CeF 3 -coated samples have five absorption peaks, and the peak intensity at 623 cm −1 is significantly higher than that at 587 cm −1 , indicating that all of the samples are Fd3̅ m disordered structures.…”

Section: ■ Introductionmentioning

confidence: 99%

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Liquid-Phase Integrated Surface Modification to Construct Stable Interfaces and Superior Performance of High-Voltage LiNi_0.5Mn_1.5O₄ Cathode Materials

Dai

et al. 2022

ACS Sustainable Chem. Eng.

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Spinel LiNi0.5Mn1.5O4 (LNMO) is regarded as the next potential generation of highly competitive cathode material for high-energy-density lithium-ion batteries due to its cobalt-free and high energy density merits. Nevertheless, the unstable surface structure and severe side reactions during cycling lead to poor electrochemical stability, limiting its commercial-scale development. Herein, a comprehensive strategy of high ionic conductivity CeF3 (CF) coating and Ce doping was achieved on an LNMO surface by a liquid-phase method to enhance its interfacial stability and electrochemical properties. The results show that the capacity retention of 1 wt %-CF-modified LNMO is 87.01% after 400 cycles at 1C and room temperature and is 83.98% after 200 cycles at 55 °C. The assembled 1 wt %-coated LNMO/Li4Ti5O12 full cell exhibited an initial discharge capacity of 99.0 mAh g–1 and capacity retention of 90.1% for 100 cycles at 0.5C. Further studies revealed that the CeF3 layer alleviated the dissolution of transition-metal ions and the side reaction between the LNMO surface and electrolyte, resulting in better structural stability, and superficial Ce doping induced an increase in Mn3+ to improve the electronic conductivity. More importantly, the CeF3 modification effectively improves its electrochemical kinetic behavior, and the fast Li+ diffusion and ideal pseudocapacitance behavior make the 1 wt %-CF electrode have optimal performance.

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Surface Design with Cation and Anion Dual Gradient Stabilizes High‐Voltage LiCoO₂

Huang

Zhao

Zhang

et al. 2022

Advanced Energy Materials

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energy density among the reported cathode materials, thus dominates the current battery market for electronics. [3,4] The practical reversible capacity of LCO is only ≈160 mA h g −1 with a cutoff voltage of 4.35 V, far below the theoretical capacity (274 mA h g −1 ), thus there is still a large space for expanding the capacity. [5,6] Further increasing the charging cutoff voltage is the most effective approach to extract more Li + from the LCO framework. [7,8] For example, La-and Al-co-doped LCO offered an initial capacity of ≈190 mA h g −1 with a cut-off voltage of 4.5 V and retained 96% capacity after 50 cycles, [9] and Ti-Mg-Al co-doped LCO offered an initial capacity of 202 mA h g −1 with a cut-off voltage of 4.6 V and retained 86% capacity after 100 cycles. [10] However, the origin of structural stability by these trace doping remains unclear, which restricts the further development of high-voltage LCO.Our recent work revealed the structural differences between regular LCO and high-voltage LCO at the atomic level, and correlated the curvature of the Co-O layers near the surface with structural instability. [11] Li's group reported a hybrid Co cation and O anion redox occurred at a high voltage of 4.6 V. [12] As shown in Scheme 1a, the generated Co 4+ and O − species at high potentials would induce the severe surface side reactions, including the catalytic decomposition of the carbonate-based electrolyte, and the lattice O loss in the form of CO 2 . Such O loss would lead to the irreversible Co migration, formation of dense Co 3 O 4 spinel phase at the surface that would block Li + diffusion, [13] and lattice distortion in the bulk evolving into microcracks upon cycling. [14] Aiming to effectively resolve these critical issues, surface engineering is proved to be a direct and efficient strategy. [15] Lu's group reported the ternary lithium, aluminum, fluorine-modified LCO with improved cycling stability when operating at 4.6 V. [16] However, the active material was covered with a large amount of Al 2 O 3 and LiAlO 2 particles rather than a uniform coating layer, and it was still susceptible to HF attack from the electrolyte, thus the interfacial stability and structural integrity deteriorated upon longterm cycling. LCO with modified surface by electrochemically stable solid electrolyte Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 was prepared through mechanical mixing followed by a high-temperature annealing process to mitigate the catalytic effect of surficial Co 4+ species at LiCoO 2 (LCO) is the most successful cathode material for commercial lithium-ion batteries. Cycling LCO to high potentials up to 4.5 V or even 4.6 V can significantly elevate the capacity but cause structural degradation due to the serious surface side reaction between the highly oxidized Co 4+ and O − species with organic electrolytes. To tackle this concern, a new strategy, constructing cation and anion dual gradients at the surface of LCO (DG-LCO), is proposed. Specifically, the electrochemically inactive cation and anion are selected to substitu...

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In situ Sr2+-doped spinel LiNi0.5Mn1.5O4 cathode material for Li-ion batteries with high electrochemical performance and its impact on morphology

Cited by 27 publications

References 60 publications

Engineering Crystal Orientation of Cathode for Advanced Lithium‐Ion Batteries: A Minireview

Engineering Crystal Orientation of Cathode for Advanced Lithium‐Ion Batteries: A Minireview

Liquid-Phase Integrated Surface Modification to Construct Stable Interfaces and Superior Performance of High-Voltage LiNi_0.5Mn_1.5O₄ Cathode Materials

Surface Design with Cation and Anion Dual Gradient Stabilizes High‐Voltage LiCoO₂

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In situ Sr2+-doped spinel LiNi0.5Mn1.5O4 cathode material for Li-ion batteries with high electrochemical performance and its impact on morphology

Cited by 27 publications

References 60 publications

Engineering Crystal Orientation of Cathode for Advanced Lithium‐Ion Batteries: A Minireview

Engineering Crystal Orientation of Cathode for Advanced Lithium‐Ion Batteries: A Minireview

Liquid-Phase Integrated Surface Modification to Construct Stable Interfaces and Superior Performance of High-Voltage LiNi0.5Mn1.5O4 Cathode Materials

Surface Design with Cation and Anion Dual Gradient Stabilizes High‐Voltage LiCoO2

Contact Info

Product

Resources

About

Liquid-Phase Integrated Surface Modification to Construct Stable Interfaces and Superior Performance of High-Voltage LiNi_0.5Mn_1.5O₄ Cathode Materials

Surface Design with Cation and Anion Dual Gradient Stabilizes High‐Voltage LiCoO₂