Exploring the origin of electrochemical performance of Cr-doped LiNi0.5Mn1.5O4

Li, Fēi; Ma, Jiani; Lin, Jianyan; Zhang, Xiaohua; Yu, Hong; Yang, Guochun

doi:10.1039/c9cp06545h

Cited by 16 publications

(11 citation statements)

References 76 publications

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“…The improved rate capability of Zr‐doped samples can be partly ascribed to the elimination of Li x Ni 1‐x O impurity, higher crystallinity, and smaller primary particle size with lower agglomeration degree. In addition, the stronger Zr−O bond can lengthen Li−O distance, making Li + ions extraction from the framework much easier, as the same case with Cr 3+ doping [14,49] . On the other hand, the surface orientation also plays an important role in the kinetics of Li + ions diffusion during charge/discharge process [41,50] .…”

Section: Resultsmentioning

confidence: 99%

“…In addition, the stronger ZrÀ O bond can lengthen LiÀ O distance, making Li + ions extraction from the framework much easier, as the same case with Cr 3 + doping. [14,49] On the other hand, the surface orientation also plays an important role in the kinetics of Li + ions diffusion during charge/discharge process. [41,50] It has been reported that the higher-surface-energy {110} and {311} facets are more favorable to Li + ions diffusion during charge/ discharge process compared with {111} and {110} facets, [41] thereby the spinel material with a higher proportion of highersurface-energy facets generally exhibits better rate capability.…”

Section: Electrochemical Performancesmentioning

confidence: 99%

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Enhanced Electrochemical Performance of 5V LiNi_0.5Mn_1.5‐xZr_xO₄ Cathode Material for Lithium‐Ion Batteries

Gong

Zhang

et al. 2021

ChemistrySelect

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Series of LiNi 0.5 Mn 1.5-x Zr x O 4 (x = 0, 0.0025, 0.005, 0.01, 0.02) samples have been prepared by a combined coprecipitationhydrothermal method followed by two-step calcination. The effects of Zr 4 + doping contents on the structure, morphology and electrochemical properties are studied. The results show that Zr 4 + doping reduces Mn 3 + content and Ni/Mn disordering degree. Additionally, Zr 4 + doping reduces primary particle size and agglomeration degree. More significantly, Zr 4 + doping leads to the appearance of higher-surface-energy {110} and/or {311} facets, while undoped sample only consists of {111} and {100} facets. But excessive Zr 4 + doping (x = 0.02) leads to the decrease of higher-surface-energy facets. Electrochemical results show that appropriate Zr 4 + doping improves the rate and cycling performances of LiNi 0.5 Mn 1.5 O 4 material. Among them, LiNi 0.5 Mn 1.495 Zr 0.005 O 4 shows the optimal electrochemical performance, which can be attributed to high phase purity, high crystallinity, appropriate primary particle size and agglomeration degree, enlarged lattice constant, and greater exposure of {110} and/or {311} facets.

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Section: Resultsmentioning

confidence: 99%

Section: Electrochemical Performancesmentioning

confidence: 99%

Enhanced Electrochemical Performance of 5V LiNi_0.5Mn_1.5‐xZr_xO₄ Cathode Material for Lithium‐Ion Batteries

Gong

Zhang

et al. 2021

ChemistrySelect

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“…Unfortunately, some coatings will cause the slow diffusion of Li, resulting in a reduction in resistance increase of the rate performance . In addition, elemental doping, such as with Al 3+ , P 5+ , Cr 3+ , and Mg 2+ , is important as an effective modification strategy for the enhancement of LNMO performance. However, the element doping strategy is often incapable of establishing a steady electrode interface on the surface of the material to resist electrolyte erosion.…”

Section: Introductionmentioning

confidence: 99%

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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“…Compared to the complicated process of coating strategies, elemental doping is more advantageous due to its cost-effectiveness. Numerous metal ions, such as Fe, Mg, Al, Zr, Cr, , Co, and Ti, − have been investigated as dopants for LNMO over the years. Although the performance of LNMO has been improved with the introduction of metal dopants into the bulk material, the mechanism of how these dopants affect the electrochemical performance is still an ongoing debate.…”

Section: Introductionmentioning

confidence: 99%

Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron

Zou

Cui

Nallan

et al. 2021

ACS Appl. Energy Mater.

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The high-voltage, cobalt-free spinel cathode LiNi0.5Mn1.5O4 (LNMO) is receiving extensive attention for lithium-ion batteries due to its low cost, high operating voltage and energy density, superior power density, and good thermal stability. However, its high operating voltage hampers its stability with commercial electrolytes and makes its practical viability challenging. We present here a Mn-rich LNMO cathode to encourage the disordering of Mn and Ni in the lattice and the incorporation of a small dose of Fe into Mn-rich LNMO (Fe-LNMO) to improve the cycling stability. The introduction of Fe further increases the cation disorder between Mn and Ni, thus enabling a better rate capability. Electron energy loss spectroscopy analysis indicates that Fe is concentrated on the surface, and X-ray photoelectron spectroscopy analysis shows that Fe-LNMO alleviates the aggressive reaction between the cathode surface and the electrolyte, thus stabilizing the interface and cycle life. Furthermore, a full cell assembled with a graphite anode with an areal capacity of 3 mA h cm–2 displays a capacity retention of 90% over 300 cycles. The present work demonstrates an effective way to promote cation disordering and lower the surface reactivity of LNMO with the electrolyte, thereby enhancing the conductivity, stabilizing the cathode–electrolyte interphase, and making LNMO promising for practical applications.

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Exploring the origin of electrochemical performance of Cr-doped LiNi_0.5Mn_1.5O₄

Abstract: Disordered LiNi0.5Mn1.5O4 has become a promising candidate for Li ion batteries due to its high specific energy.

Cited by 16 publications

References 76 publications

Enhanced Electrochemical Performance of 5V LiNi_0.5Mn_1.5‐xZr_xO₄ Cathode Material for Lithium‐Ion Batteries

Enhanced Electrochemical Performance of 5V LiNi_0.5Mn_1.5‐xZr_xO₄ Cathode Material for Lithium‐Ion Batteries

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

Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron

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Exploring the origin of electrochemical performance of Cr-doped LiNi0.5Mn1.5O4

Abstract: Disordered LiNi0.5Mn1.5O4 has become a promising candidate for Li ion batteries due to its high specific energy.

Cited by 16 publications

References 76 publications

Enhanced Electrochemical Performance of 5V LiNi0.5Mn1.5‐xZrxO4 Cathode Material for Lithium‐Ion Batteries

Enhanced Electrochemical Performance of 5V LiNi0.5Mn1.5‐xZrxO4 Cathode Material for Lithium‐Ion Batteries

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

Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron

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Exploring the origin of electrochemical performance of Cr-doped LiNi_0.5Mn_1.5O₄

Enhanced Electrochemical Performance of 5V LiNi_0.5Mn_1.5‐xZr_xO₄ Cathode Material for Lithium‐Ion Batteries

Enhanced Electrochemical Performance of 5V LiNi_0.5Mn_1.5‐xZr_xO₄ Cathode Material for Lithium‐Ion Batteries

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