Double the Capacity of Manganese Spinel for Lithium‐Ion Storage by Suppression of Cooperative Jahn–Teller Distortion

Zuo, Changjian; Hu, Zongxiang; Qi, Rui; Liu, Jiajie; Li, Zhibo; Lu, Junliang; Dong, C.; Yang, Kai; Huang, Weiyuan; Chen, Cong; Song, Zhibo; Song, Sicheng; Yu, Yaoming; Zheng, Jiaxin; Pan, Feng

doi:10.1002/aenm.202000363

Cited by 98 publications

(63 citation statements)

References 43 publications

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“…This leads to the distinct evolution of voltage regions near 4 V and 3 V, [64,65] similar to what was observed on metastable DRX materials such as Li 4 Mn 2 O 5 . [66][67][68] The arrangements not only create excellent percolation pathways of low activation energy Li migration channels [69][70][71] but also mitigate Jahn-teller distortion and enhance structural stability, [63,72] leading to better material utilization at a given current density, increased accessible capacity and more than 100% of capacity retention with cycling. It is conceivable that over-lithiation of the off-stoichiometry spinel-like domains occurs upon discharging below 3 V, enabling additional capacity not accounted in the pristine material and contributing to additional discharge capacity.…”

Section: Discussionmentioning

confidence: 99%

Exceptional Cycling Performance Enabled by Local Structural Rearrangements in Disordered Rocksalt Cathodes

Ahn

Satish

et al. 2022

Advanced Energy Materials

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cost and thermal stability of Mn. [4] However, both families of cathodes face significant challenges in maintaining their structural integrity and rate capability upon cycling, with rapid capacity fade, significant voltage hysteresis, and impedance rise often accompanying the gradual transformation in local and/or long-range structure upon Li (de)intercalation. [5][6][7][8] At the material level, side reactions with the electrolyte, TM reduction and dissolution, TM migration and structural transformation as well as irreversible O redox chemistry, have all been suggested to contribute to these issues. [9][10][11][12][13][14][15] To minimize capacity loss in DRX, increasing Mn redox contribution at the expense of O-based redox processes is an effective strategy, as the former chemistry is inherently more reversible than the latter. [15][16][17][18] Fluorine substitution into the O anion sublattice not only stabilizes O redox, as shown by a number of recent studies, [10,[18][19][20][21][22] but also lowers the overall anionic valence and allows for an increased amount of Mn to be incorporated into the material. In contrast to the layered structure, F substitution into the cubic DRX structure can easily be achieved during synthesis. Substitution levels up to 10 at.% and 33 at.% have previously been reported on fluorinated Mn-based DRX samples prepared by solid-state and high-energy ball milling synthesis methods, respectively. [10,18,19,20] Although electrochemical performance improvements have been observed even at low levels of FThe capacity of lithium transition-metal (TM) oxide cathodes is directly linked to the magnitude and accessibility of the redox reservoir associated with TM cations and/or oxygen anions, which traditionally decreases with cycling as a result of chemical, structural, or mechanical fatigue. Here, it is shown that a capacity increase over 125% can be achieved upon cycling of high-energy Mn-and F-rich cation-disordered rocksalt oxyfluoride cathodes. This study reveals that in Li 1.2 Mn 0.7 Nb 0.1 O 1.8 F 0.2 , repeated Li extraction/reinsertion utilizing Mn 3+ /Mn 4+ redox along with some degree of O-redox participation leads to local structural rearrangements and formation of domains with off-stoichiometry spinel-like features. The effective integration of these local "structure-domains" within the cubic disordered rocksalt framework promotes better Li diffusion and improves material utilization, consequently increased capacity upon cycling. This study provides important new insights into materials design strategies to further exploit the rich compositional and structural space of Mn chemistry for developing sustainable, high-energy cathode materials.

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Section: Discussionmentioning

confidence: 99%

Exceptional Cycling Performance Enabled by Local Structural Rearrangements in Disordered Rocksalt Cathodes

Ahn

Satish

et al. 2022

Advanced Energy Materials

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“…[ 5 ] revealed that the 16 d sites in the spinel LNMO can be partially occupied by Ti 4+ , providing longer cycle life. One further work [ 24 ] on the LiMn 2 O 4 cathode, which is isostructural to LNMO, shows that the substitution of Mn with Li at 16 d sites in the LiMn 2 O 4 material significantly suppresses the cooperative Jahn–Teller effects as a result of the increased cationic disorder. Considering the similarity between LNMO and LiMn 2 O 4 structures, this further supports the strategy to target 16 d sites to reduce Mn dissolution in high‐voltage LNMO.…”

Section: Introductionmentioning

confidence: 99%

Crystallographic‐Site‐Specific Structural Engineering Enables Extraordinary Electrochemical Performance of High‐Voltage LiNi_0.5Mn_1.5O₄ Spinel Cathodes for Lithium‐Ion Batteries

Liang

Peterson

et al. 2021

Advanced Materials

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The development of reliable and safe high‐energy‐density lithium‐ion batteries is hindered by the structural instability of cathode materials during cycling, arising as a result of detrimental phase transformations occurring at high operating voltages alongside the loss of active materials induced by transition metal dissolution. Originating from the fundamental structure/function relation of battery materials, the authors purposefully perform crystallographic‐site‐specific structural engineering on electrode material structure, using the high‐voltage LiNi0.5Mn1.5O4 (LNMO) cathode as a representative, which directly addresses the root source of structural instability of the Fdm structure. By employing Sb as a dopant to modify the specific issue‐involved 16c and 16d sites simultaneously, the authors successfully transform the detrimental two‐phase reaction occurring at high‐voltage into a preferential solid‐solution reaction and significantly suppress the loss of Mn from the LNMO structure. The modified LNMO material delivers an impressive 99% of its theoretical specific capacity at 1 C, and maintains 87.6% and 72.4% of initial capacity after 1500 and 3000 cycles, respectively. The issue‐tracing site‐specific structural tailoring demonstrated for this material will facilitate the rapid development of high‐energy‐density materials for lithium‐ion batteries.

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“…It is interesting to note that the higher Mn 4+ /Mn 3+ ratio (5 in our case) suggests structural stability. [34][35][36] Therefore, the Mn 4+ LiMn 2 O 4 spinel. For this reason, the stronger bonds of the octahedron MO 6 can be prevented from dissolving Mn, maintains structural stability, and allows a higher Li + diffusion during the electrochemical cycle, so that the cycling stability and the velocity capacity of our sample are improved.…”

Section: Phase Identification Resultsmentioning

confidence: 99%

Molten salt synthesis of LiMn ₁ _. ₂ Ni ₀ _. ₃ Cr ₀ _. ₁ Co ₀

Iffer¹,

Belaı̈che²,

Elansary³

et al. 2021

Intl J of Energy Research

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The molten salt synthesis method became an excellent synthesis technique to elaborate nanomaterials because of its meritorious advantages including low cost, easy to scale up, simple to operate, and environmental friendliness. For this reason, the compound LiMn 1.2 Ni 0.3 Cr 0.1 Co 0.15 Al 0.23 La 0.02 O 4 was synthesized for the first time by molten salt method using NaCl as the salt and a nonstandard manganese source with metallurgical grade. The obtained cathode material was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transformer infra-red (FT-IR), and electrochemical characterization. XRD and FT-IR results confirm the stability and formation of pure spinel phase without any impurities. TEM images showed that the spinel synthesized phase consists of 77 to 135 nm-sized polyhedral nanoparticles. The cyclic voltammogram results showed that the synthesized spinel cathode material exhibits two-main redox peaks at 4.06/3.9 V and 3.1/2.8 V vs Li + /Li, which indicate the possibility of insertion of extra lithium in the spinel structure. Galvanostatic charge-discharge studies were also carried out showed that the prepared spinel material has two discharge plateaus in the potential window of 1.5 to 5 V and a discharge capacity of 179 mAh g À1 at 0.1 C, which is higher than the theoretical value which confirms the insertion of extra lithium in the spinel structure and enhance the capacity of the cathode material. The electrochemical impedance spectroscopy was performed, and the Li-ion diffusion coefficient was also calculated.

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Double the Capacity of Manganese Spinel for Lithium‐Ion Storage by Suppression of Cooperative Jahn–Teller Distortion

Cited by 98 publications

References 43 publications

Exceptional Cycling Performance Enabled by Local Structural Rearrangements in Disordered Rocksalt Cathodes

Exceptional Cycling Performance Enabled by Local Structural Rearrangements in Disordered Rocksalt Cathodes

Crystallographic‐Site‐Specific Structural Engineering Enables Extraordinary Electrochemical Performance of High‐Voltage LiNi_0.5Mn_1.5O₄ Spinel Cathodes for Lithium‐Ion Batteries

Molten salt synthesis of LiMn ₁ _. ₂ Ni ₀ _. ₃ Cr ₀ _. ₁ Co ₀

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Double the Capacity of Manganese Spinel for Lithium‐Ion Storage by Suppression of Cooperative Jahn–Teller Distortion

Cited by 98 publications

References 43 publications

Exceptional Cycling Performance Enabled by Local Structural Rearrangements in Disordered Rocksalt Cathodes

Exceptional Cycling Performance Enabled by Local Structural Rearrangements in Disordered Rocksalt Cathodes

Crystallographic‐Site‐Specific Structural Engineering Enables Extraordinary Electrochemical Performance of High‐Voltage LiNi0.5Mn1.5O4 Spinel Cathodes for Lithium‐Ion Batteries

Molten salt synthesis of LiMn 1 . 2 Ni 0 . 3 Cr 0 . 1 Co 0

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Crystallographic‐Site‐Specific Structural Engineering Enables Extraordinary Electrochemical Performance of High‐Voltage LiNi_0.5Mn_1.5O₄ Spinel Cathodes for Lithium‐Ion Batteries

Molten salt synthesis of LiMn ₁ _. ₂ Ni ₀ _. ₃ Cr ₀ _. ₁ Co ₀