Investigation of the self-discharge behaviors of the LiMn2O4 cathode at elevated temperatures: in situ X-ray diffraction analysis and a co-doping mitigation strategy

Tang, Xiaoyu; Zhou, Jie; Bai, Miao; Wu, Weiwei; Li, Shaowen; Ma, Yanwei

doi:10.1039/c9ta02718a

Cited by 52 publications

(39 citation statements)

References 44 publications

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“…[ 14 ] However, PEO with ether groups at the interface of NCM||SPE is easy to lose electrons during periodic rest or storage, accompanied with Li + inserted into NCM to remain charge balance, especially in high‐temperature environments. [ 16 ] Such a series of interface side reactions may result in increasing of Rct with the growth of CEI thickness, causing the voltage and capacity rapid decay after charge.…”

Section: Resultsmentioning

confidence: 99%

“…[ 14 ] In practical applications (such as portable electronics and electric vehicles), batteries are unlikely to be continuous operation without rest. [ 15 ] However, PEO with ether groups tends to lose electrons above 4.00 V, [ 16 ] Li + would insert into cathode active materials simultaneously for the charge balance during periodic rest or storage, [ 17 ] which results in increasing of the charge transfer resistance (Rct) with the growth of cathode electrolyte interface (CEI) thickness, exacerbating the deterioration of interfacial structure stability. [ 18 ] Such a detrimental behavior causes high irreversible capacity and low coulombic efficiency (CE), further engendering the failure of ASSLBs.…”

Section: Introductionmentioning

confidence: 99%

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Constructing Interfacial Nanolayer Stabilizes 4.3 V High‐Voltage All‐Solid‐State Lithium Batteries with PEO‐Based Solid‐State Electrolyte

Wang

Song

Jiang

et al. 2022

Adv Funct Materials

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The complicated interfacial problems of poly(ethylene oxide) (PEO)‐based solid polymer electrolytes (SPEs) at high voltages severely hinder its practical applications for high‐energy‐density all‐solid‐state lithium batteries (ASSLBs). Herein, the failure mechanisms of ASSLBs with LiNi0.6Co0.2Mn0.2O2 (NCM)‐PEO are studied. It is found that the ASSLBs after charge generates a sharp drop of 0.62 V at the cut‐off voltage of 4.30 V, and induce a high interfacial resistance due to forming an uneven thick cathode electrolyte interface on the NCM surface, as well as cause the destruction of NCM surface structure during storage, leading to serious performance degradation. Constructing the interfacial nanolayer with aromatic polyamide (APA) on the surface of NCM active particles (NCM@APA) can mitigate interfacial side reactions between NCM and SPE. Robust interfacial nanolayers not only effectively protect the crystal structure of NCM but also provide a steady interfacial environment for Li+ diffusion kinetics. Accordingly, NCM@APA||SPE||Li ASSLBs exhibit an acceptable voltage drop of 0.27 V after 10 days storage and a substantially improved electrochemical performance with an average coulombic efficiency of 99.1% and capacity retention of 76.7% at 30 mA g−1 after 80 cycles.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Constructing Interfacial Nanolayer Stabilizes 4.3 V High‐Voltage All‐Solid‐State Lithium Batteries with PEO‐Based Solid‐State Electrolyte

Wang

Song

Jiang

et al. 2022

Adv Funct Materials

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“…No secondary phases are observed in C-NMC811, possibly due to too small of a signal from the coating material as well as some peak overlap. Furthermore, both samples exhibit good crystallinity, as indicated by the well-defined (018) and (110) double peaks and low cation mixing based on the I (003) / I (104) ratio close to 1.2. − It is observed that the intensity ratio for C-NMC811 is slightly lower than that of NMC811. This may be due to incomplete lithiation of the Ni-rich component of the C-NMC811 hydroxide precursor.…”

Section: Resultsmentioning

confidence: 88%

Modified Nickel-Rich Cathodes via Conformal Nanoparticle Coating of Precursors Using a Single Reactor Process

Azhari

Arsenault

Gao

et al. 2021

ACS Appl. Energy Mater.

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Ni-rich LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode materials, with a higher energy density compared to current commercial cathodes, are looked upon as the next improvement in lithium-ion batteries. However, modifications are needed to address issues of capacity fading due to a variety of degradation mechanisms, most of which initiate at the cathode/ electrolyte interface. In this work, this issue is addressed by modifying a typical coprecipitation method to develop a heterogeneous precursor composed of transition-metal hydroxides coated with nanoparticles of composition Mn 2.7 Co 0.3 O 4 . Reactor conditions and feedstock are altered to induce nanoparticle formation directly after NMC811 hydroxide secondary particle formation, with pH, feedstock solution, and reaction time being significant factors. The lithiated and sintered cathode maintains a high initial capacity of ∼215 mAh/g because of the Ni-rich base material and an improvement of capacity retention of over 40% at both 25 and 55 °C temperatures due to a conformal nanoscale coating of LiMn 1.8 Co 0.2 O 4 spinel material. Electrochemical analysis combined with transmission electron microscopy indicates that improvements are attributed to the suppression of impedance growth by reducing undesirable reactions between the Ni-rich cathode and electrolyte in the highly discharged state. This work demonstrates a practical method for synthesizing spinel-coated NMC during initial precursor synthesis as a step toward high-throughput commercialization of Ni-rich NMC cathodes.

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“…(LMO), in-situ XRD data revealed the structural changes during various self-discharge regions of charged LMO cathode [42]. The result illustrated that two slow voltage slopes with a following sharp drop corresponding to two-phase transition, solid-solution reaction and the migration of electric double-layer ions, respectively.…”

Section: In-situ/operando Xrdmentioning

confidence: 96%

In-situ/operando characterization techniques in lithium-ion batteries and beyond

Guo

Zhou

2021

Journal of Energy Chemistry

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Investigation of the self-discharge behaviors of the LiMn₂O₄ cathode at elevated temperatures: in situ X-ray diffraction analysis and a co-doping mitigation strategy

Abstract: The lithium ion re-intercalated into the LiMn2O4 lattice during self-discharge.

Cited by 52 publications

References 44 publications

Constructing Interfacial Nanolayer Stabilizes 4.3 V High‐Voltage All‐Solid‐State Lithium Batteries with PEO‐Based Solid‐State Electrolyte

Constructing Interfacial Nanolayer Stabilizes 4.3 V High‐Voltage All‐Solid‐State Lithium Batteries with PEO‐Based Solid‐State Electrolyte

Modified Nickel-Rich Cathodes via Conformal Nanoparticle Coating of Precursors Using a Single Reactor Process

In-situ/operando characterization techniques in lithium-ion batteries and beyond

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