Correlating cycle performance improvement and structural alleviation in LiMn2-xMxO4 spinel cathode materials: A systematic study on the effects of metal-ion doping

Gu, Heyun; Wang, Guangjin; Zhu, Chengwei; Hu, Ye; Zhang, Xinming; Wen, Wen; Yang, Xiaowei; Wang, Baofeng; Gao, Xiang; Zhan, Xiaoli; Li, Jingkun; Ma, Zi-Feng; He, Qinggang

doi:10.1016/j.electacta.2018.12.152

Cited by 30 publications

(12 citation statements)

References 69 publications

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“…34,35 As seen in Figure 2c,d, the fitted results show that the atomic content of Mn 4+ increases from 49.82 to 52.68%, while that of Mn 3+ reduces from 50.18 to 47.32% because of the Al 3+ ion (x = 0.05) doping, which suggests that the substitution of Al for Mn in LiMn 2 O 4 can reduce the content of Mn 3+ , being beneficial for restraining the Jahn− Teller effect of the [MnO 6 ] octahedron and stabilizing the LiMn 2 O 4 structure. 36 3.2. Structure Evolution of Al-Doped LiMn 2 O 4 at the Atomic Scale.…”

Section: Resultsmentioning

confidence: 99%

“…In this work, the Mn 2p 3/2 binding energies of LiMn 2 O 4 and LiAl 0.05 Mn 1.95 O 4 are also in this range (Figure b), which suggests that the Mn oxidation states are between +3 and +4. To obtain the detailed information for the valence state of Mn in the LiMn 2 O 4 and LiAl 0.05 Mn 1.95 O 4 samples, we performed peak fitting for the Mn 2p 3/2 peaks by CasaXPS software (Tables S2 and S3 show the fitting parameters). , As seen in Figure c,d, the fitted results show that the atomic content of Mn 4+ increases from 49.82 to 52.68%, while that of Mn 3+ reduces from 50.18 to 47.32% because of the Al 3+ ion ( x = 0.05) doping, which suggests that the substitution of Al for Mn in LiMn 2 O 4 can reduce the content of Mn 3+ , being beneficial for restraining the Jahn–Teller effect of the [MnO 6 ] octahedron and stabilizing the LiMn 2 O 4 structure …”

Section: Results and Discussionmentioning

confidence: 99%

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Understanding the Effect of Al Doping on the Electrochemical Performance Improvement of the LiMn₂O₄ Cathode Material

Zheng

Cheng

et al. 2021

ACS Appl. Mater. Interfaces

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It is well known that the electrochemical performance of spinel LiMn2O4 can be improved by Al doping. Herein, combining X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM) with in situ electron-beam (E-beam) irradiation techniques, the influence of Al doping on the structural evolution and stability improvement of the LiMn2O4 cathode material is revealed. It is revealed that an appropriate concentration of Al3+ ions could dope into the spinel structure to form a more stable LiAl x Mn2–x O4 phase framework, which can effectively stabilize the surface and bulk structure by inhibiting the dissolution of Mn ions during cycling. The optimized LiAl0.05Mn1.95O4 sample exhibits a superior capacity retention ratio of 80% after 1000 cycles at 10 C (1 C = 148 mA h g–1) in the voltage range of 3.0–4.5 V, which possesses an initial discharge capacity of 90.3 mA h g–1. Compared with the undoped LiMn2O4 sample, the Al-doped sample also shows superior rate performance, especially the capacity recovery performance.

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Section: Resultsmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Understanding the Effect of Al Doping on the Electrochemical Performance Improvement of the LiMn₂O₄ Cathode Material

Zheng

Cheng

et al. 2021

ACS Appl. Mater. Interfaces

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“…To solve the aforementioned problems, many methods have been studied and utilized. Element doping is an effective method to improve the cycling performance of LiMn 2 O 4 and includes metal-ion doping (Al 3+ , Cr 3+ , Mg 2+ , Ni 2+ ), − nonmetal ion doping (Si 4+ , F – ), , and ionic codoping. − Gu et al studied the electrochemical performance of LiMn 2– x M x O 4 (M = Mn, Co, Ni, Fe, Cr, Al; x = 0.05, 0.1, 0.15, and 0.2) and showed that doping of metal ions effectively blocks the crystal phase transition, reducing the microstrain and volume contractions during the cycling process. Furthermore, LiMn 2– x M x O 4 exhibited better electrochemical stability and less capacity fading than LiMn 2 O 4 did.…”

Section: Introductionmentioning

confidence: 99%

Enhancing the Electrochemical Properties of Ti-Doped LiMn₂O₄ Spinel Cathode Materials Using a One-Step Hydrothermal Method

et al. 2021

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In this study, LiMn 2– x Ti x O 4 cathode materials were synthesized by a simple one-step hydrothermal method, and the effects of Ti doping on the sample structure and electrochemical properties were examined. The results indicated that Ti doping did not affect the spinel structure of LiMn 2 O 4 , and no other hybrid phases were produced. Furthermore, appropriate doping with Ti improved the particle uniformity of the samples. The electrochemical performance results showed that LiMn 1.97 Ti 0.03 O 4 exhibited much better cycling performance than the undoped sample. The discharge capacity of LiMn 1.97 Ti 0.03 O 4 reached 136 mAh g –1 at 25 °C at 0.2C, and the specific capacity reached 106.2 mAh g –1 after 300 cycles, with a capacity retention rate of 78.09%. Additionally, the specific capacity of LiMn 1.97 Ti 0.03 O 4 was 102.3 mAh g –1 after 100 cycles at 55 °C, with a capacity retention rate of 75.44%. The Ti-doped samples thus exhibited an impressive high-rate performance. The discharge capacity of LiMn 2 O 4 was only 31.3 mAh g –1 at 10C, while the discharge-specific capacity of LiMn 1.97 Ti 0.03 O 4 reached 73.4 mAh g –1 . Furthermore, to assess the higher Li + diffusion coefficient and lower internal resistance of the Ti-doped samples, cyclic voltammetry and impedance spectra data were obtained. Our results showed that Ti doping enhanced the crystal structure of LiMn 2 O 4 and improved Li + diffusion, resulting in significant improvements in the cycling and rate performance of Ti-doped samples.

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“…Specifically, the peaks of the Fe‐doped samples were shifted to lower angles with increasing Fe doping concentrations (Figure 3d). Based on Bragg's law, the low angle shift in the Fe‐doped LMO samples may have resulted from the replacement of Mn 3+ (0.64 Å) by Fe 3+ (0.65 Å) [30,39] . With increasing Fe doping, the peak intensity of the (111) plane decreased (Table 2).…”

Section: Resultsmentioning

confidence: 99%

“…Based on Bragg's law, the low angle shift in the Fedoped LMO samples may have resulted from the replacement of Mn 3 + (0.64 Å) by Fe 3 + (0.65 Å). [30,39] With increasing Fe doping, the peak intensity of the (111) plane decreased (Table 2). This implies that doping could affect the growth of the truncated octahedral shape with the dominant {111} facets, consistent with the SEM analysis.…”

Section: Resultsmentioning

confidence: 99%

Enhanced Cycling Performance of Fe‐doped LiMn₂O₄ Truncated Octahedral Cathodes for Li‐Ion Batteries

et al. 2022

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LiMn 2 O 4 (LMO) with a spinel crystal structure is a promising cathode for next-generation Li-ion batteries (LIBs), owing to its low cost and high operating voltage of ~4.4 V. However, due to the Jahn-Teller distortion effect, LMO typically exhibits deteriorated cycling performance, owing to the dissolution of Mn into a liquid electrolyte. In this study, Fe-doped truncated octahedral LMO cathodes with different concentrations were synthesized to improve LMO stability in LIBs. The Fe-doped truncated octahedral LMO was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The Li + ion diffusion coefficients of the cathodes were measured using electrochemical impedance spectroscopy and the galvanostatic intermittent titration technique. Compared to the truncated octahedral undoped LMO, the Fe-doped LMO cathode with an appropriate amount of dopant exhibited the best LIB performance, with the highest Li + ion diffusivity resulting from the increased oxygen vacancy as the path of Li + ion.

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Correlating cycle performance improvement and structural alleviation in LiMn2-xMxO4 spinel cathode materials: A systematic study on the effects of metal-ion doping

Cited by 30 publications

References 69 publications

Understanding the Effect of Al Doping on the Electrochemical Performance Improvement of the LiMn₂O₄ Cathode Material

Understanding the Effect of Al Doping on the Electrochemical Performance Improvement of the LiMn₂O₄ Cathode Material

Enhancing the Electrochemical Properties of Ti-Doped LiMn₂O₄ Spinel Cathode Materials Using a One-Step Hydrothermal Method

Enhanced Cycling Performance of Fe‐doped LiMn₂O₄ Truncated Octahedral Cathodes for Li‐Ion Batteries

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Correlating cycle performance improvement and structural alleviation in LiMn2-xMxO4 spinel cathode materials: A systematic study on the effects of metal-ion doping

Cited by 30 publications

References 69 publications

Understanding the Effect of Al Doping on the Electrochemical Performance Improvement of the LiMn2O4 Cathode Material

Understanding the Effect of Al Doping on the Electrochemical Performance Improvement of the LiMn2O4 Cathode Material

Enhancing the Electrochemical Properties of Ti-Doped LiMn2O4 Spinel Cathode Materials Using a One-Step Hydrothermal Method

Enhanced Cycling Performance of Fe‐doped LiMn2O4 Truncated Octahedral Cathodes for Li‐Ion Batteries

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Product

Resources

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Understanding the Effect of Al Doping on the Electrochemical Performance Improvement of the LiMn₂O₄ Cathode Material

Understanding the Effect of Al Doping on the Electrochemical Performance Improvement of the LiMn₂O₄ Cathode Material

Enhancing the Electrochemical Properties of Ti-Doped LiMn₂O₄ Spinel Cathode Materials Using a One-Step Hydrothermal Method

Enhanced Cycling Performance of Fe‐doped LiMn₂O₄ Truncated Octahedral Cathodes for Li‐Ion Batteries