Understanding the Effect of Al Doping on the Electrochemical Performance Improvement of the LiMn<sub>2</sub>O<sub>4</sub> Cathode Material

Xu, Wangqiong; Zheng, Yonghui; Cheng, Yan; Qi, Ruijuan; Peng, Hui; Lin, Hechun; Huang, Rong

doi:10.1021/acsami.1c11315

Cited by 59 publications

(43 citation statements)

References 51 publications

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“…The report of Peng Li et al has shown that doping of Al 3+ to a certain limit can reduce the capacity and increase the stability, 29 and the reports of C.Peng et al and Xu et al have shown that the capacity decays if the Al 3+ ratio increases. 36,37 The same behavior is observed in our materials.…”

Section: Electrochemical Characterizationsupporting

confidence: 88%

“…Though, the presence of Al in the structure helps in stability rather than improving the discharge capacity. 31,36,37,57 EIS studies were performed with two-electrode system for the fresh cells to know the interface resistance and kinetics of the Li + insertion/exertion mechanism. The obtained data have been fitted with the equivalent circuit, which is provided in the inset of Figure 5b, where R1 represents the Ohmic resistance due to the electrochemical system (R s ), R 2 represents the resistance of the SEI (R SEI ), R 3 represents the chargetransfer resistance (R ct ), CPE represents the constant phase element (Q), and W is the Warburg diffusion impedance (W).…”

Section: Electrochemical Characterizationmentioning

confidence: 99%

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Formation of the Secondary Phase Domain by Multi-Cation Substitution for the Superior Electrochemical Performance of Spinel Cathodes for High-Voltage Li-Ion Batteries

Shivamurthy

Thripuranthaka

Shelke

et al. 2022

ACS Appl. Energy Mater.

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Disorder-structured spinel oxides are opening frontiers for high-capacity/high-voltage cathodes to meet the challenges of independence on cobalt-containing cathodes toward cheap and sustainable energy storage sources in Li-ion batteries (LIBs). In the present work, a series of Co-free materials: LiMn 2-x-y-z Ni x Fe y Al z O 4 (x = 0.8−0.5, y = 0.1−0.25, and z = 0.1−0.25) with spinel/rock salt disordered structures are reported. The refinement studies confirmed that the materials synthesized are of mixed phase, and the I 311 /I 400 peaks ratio confirms that the synthesized materials are stable enough for electrochemical applications. This article addresses the influence of the secondary phase on the electrochemical activity and the reduction of the Mn 3+ ratio to alleviate the Mn dissolution issue for bettered stability. The optimized LiMnNi 0.7 Fe 0.1 Al 0.2 O 4 is appraised as a cathode material in the voltage range between 3.5 and 5 V (vs. Li + /Li) with an initial discharge capacity of 148.7 mA h g −1 at a rate of 1 C. This material showed very good cycling stability with a capacity retention of 79.5% after 1000 cycles. The cyclic voltammetry studies showed that the material can be a potential candidate for 5 V applications.

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Section: Electrochemical Characterizationsupporting

confidence: 88%

Section: Electrochemical Characterizationmentioning

confidence: 99%

Formation of the Secondary Phase Domain by Multi-Cation Substitution for the Superior Electrochemical Performance of Spinel Cathodes for High-Voltage Li-Ion Batteries

Shivamurthy

Thripuranthaka

Shelke

et al. 2022

ACS Appl. Energy Mater.

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“…LiZn x Mn 2– x O 4 (0 ≤ x ≤ 0.1) octahedron particles are prepared by a hydrothermal treatment and calcination process, as reported in our previous studies. − First, to obtain Mn 3 O 4 nanoparticles with better reaction activity and smaller particles, commercially purchased Mn 3 O 4 powders (1.0 g) were dispersed into a NaOH aqueous solution (30 mL, 5 mol dm –3 ) with magnetic stirring for 1 h. Afterward, the dispersion was transferred to a Teflon-lined stainless-steel autoclave (50 mL) and heated at 205 °C for 4 days in an oven. The final precipitated products were collected and washed repeatedly with deionized water.…”

Section: Methodsmentioning

confidence: 99%

In Situ Formed Core–Shell LiZn_xMn_2–xO₄@ZnMn₂O₄ as Cathode for Li-Ion Batteries

Song

et al. 2022

ACS Appl. Mater. Interfaces

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Elemental doping and surface modification are commonly used strategies for improving the electrochemical performance of LiMn2O4, such as the rated capacity and cycling stability. In this study, in situ formed core–shell LiZn x Mn2–x O4@ZnMn2O4 cathodes are prepared by tuning the Zn-doping content. Through comprehensive microstructural analyses by the spherical aberration-corrected scanning transmission microscopy (Cs-STEM) technique, we shed light on the correlation between the microstructural configuration and the electrochemical performance of Zn-doped LiMn2O4. We demonstrate that part of Zn2+ ions dope into the spinel to form LiZn x Mn2–x O4 in bulk and other Zn2+ ions occupy the 8a sites of the spinel to form the ZnMn2O4 shell on the outermost surface. This in situ formed core–shell LiZn x Mn2–x O4@ZnMn2O4 contributes to better structural stabilization, presenting a superior capacity retention ratio of 95.8% after 700 cycles at 5 C at 25 °C for the optimized sample (LiZn0.02Mn1.98O4), with an initial value of 80 mAh g–1. Our investigations not only provide an effective way toward high-performance LIBs but also shed light on the fundamental interplay between the microstructural configuration and the electrochemical performance of Zn-doped spinel LiMn2O4.

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“…Up to now, researchers have carried out a wide range of studies to mitigate Mn dissolution, including modulation of particle morphology, changing electrolyte components, coating, , and doping. , Since doping can affect the intrinsic stability of the material by regulating the interaction between atoms, we chose to study the effects of (surface) doping on Mn dissolution of the LMO cathode. Taking the 3.5+ nominal valence of Mn ions in the LMO cathode as the demarcation, the dopants that have been studied can be divided into two categories: (1) elements with 2+/3+ nominal valence such as Mg, Al, , Cu, Zn, and so forth. Researchers believe that these elements can reduce the proportion of Mn 3+ in the LMO cathode, thus reducing the deterioration of the LMO cathode properties due to the disproportionation reaction and the John–Teller effect. , (2) Elements with nominal valence higher than 3+ such as Ti, V, Cr, Nb, , and so forth.…”

Section: Introductionmentioning

confidence: 99%

Screening LiMn₂O₄ Surface Modification Schemes under Theoretical Guidance

Sun

Xiao

et al. 2022

ACS Appl. Mater. Interfaces

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Mn dissolution is one of the most important factors for the failure of LiMn2O4 batteries. Doping has been widely adopted in the modification of LiMn2O4 cathodes; however, there is still a lack of theoretical guidance on screening the dopants. Here, through first-principles calculations, we systematically investigated the effects of all 3, 4d transition metals as well as Mg, Ca, Sr, Al, Ga, and In on the surface oxygen stability of LiMn2O4 cathodes, which has been proved to be correlated with the stability of the surface Mn atoms. Six competitive dopants, namely Nb, Ru, Mo, V, Tc, and Ti, were screened out. Besides, for three dopants in low valence states (Mg, Cu, and Zn), their Li-site doping can more effectively stabilize the surface oxygen atoms compared with Mn-site doping. Finally, we synthesized LiMn2O4 samples with Mg, Mo, and Nb surface doping to validate the rationality of the computational results. We found that particle morphology should also be considered in addition to surface oxygen stability for controlling Mn dissolution. Moreover, the electrochemical performance of LiMn2O4 batteries is a more complex issue and cannot be solely regulated by Mn dissolution. During the experiments, we have explored novel efficient binary chromogenic reagents for ultraviolet–visible spectroscopy analysis that can be used for rapid and low-cost Mn dissolution detection. This work provides a paradigm for the systematic design of the surface modification of the LiMn2O4 cathode under theoretical guidance.

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

Cited by 59 publications

References 51 publications

Formation of the Secondary Phase Domain by Multi-Cation Substitution for the Superior Electrochemical Performance of Spinel Cathodes for High-Voltage Li-Ion Batteries

Formation of the Secondary Phase Domain by Multi-Cation Substitution for the Superior Electrochemical Performance of Spinel Cathodes for High-Voltage Li-Ion Batteries

In Situ Formed Core–Shell LiZn_xMn_2–xO₄@ZnMn₂O₄ as Cathode for Li-Ion Batteries

Screening LiMn₂O₄ Surface Modification Schemes under Theoretical Guidance

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

Cited by 59 publications

References 51 publications

Formation of the Secondary Phase Domain by Multi-Cation Substitution for the Superior Electrochemical Performance of Spinel Cathodes for High-Voltage Li-Ion Batteries

Formation of the Secondary Phase Domain by Multi-Cation Substitution for the Superior Electrochemical Performance of Spinel Cathodes for High-Voltage Li-Ion Batteries

In Situ Formed Core–Shell LiZnxMn2–xO4@ZnMn2O4 as Cathode for Li-Ion Batteries

Screening LiMn2O4 Surface Modification Schemes under Theoretical Guidance

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Product

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

In Situ Formed Core–Shell LiZn_xMn_2–xO₄@ZnMn₂O₄ as Cathode for Li-Ion Batteries

Screening LiMn₂O₄ Surface Modification Schemes under Theoretical Guidance