Atomically Interlocked Chemistry Activated by Interstitial Sites in LiMn₂O₄ Cathode

Abstract

The extensive applications of spinel LiMn2O4 (LMO) are severely plagued by grievous capacity degradation and structural collapse, mainly ascribed to deleterious Jahn−Teller distortion and subsequent dissolution of Mn2+. Herein, highly stable LMO with atomic interlocking effect is rationally designed via engineering Al into the unoccupied 16c sites. The local coordination environment of the surficial MnO6 octahedron is reconstructed by robust Al−O band coherency, giving strengthened lattice oxygen skeleton and constraining heterophase evolution with the suppression of Jahn−Teller distortion, validated by theoretical calculations coupled with synchrotron X‐ray absorption spectrum. Concomitantly, with the occupation of Al in interstitial site, the migration of Mn is effectively restrained, directly observed by scanning transmission electron microscopy, leading to the inhibition of inactivation as well as dissolution loss of Mn. Resultantly, splendid long cycling stability of Al‐LMO after 1000 loops with only 0.019% capacity fading per cycle is presented. Given this, this elaborate study can provide an ingenious avenue for regulating the structure/interface chemistry architecture in electrode materials.

Fundamentals, status and challenges of direct recycling technologies for lithium ion batteries

“…17a. 225 A clear phase transition turning point is observed above 4.05 V and when further charged to 4.3 V, it transforms into soluble Mn 3 O 4 and Li 4 Mn 5 O 12 , which causes internal stress. During discharge, Li 2 MnO 4 is formed due to uneven Li + intercalation, and a serious Jahn-Teller effect is induced due to the increase in the amount of Mn 3+ (Fig.…”

In Situ Construction of High‐Density Solid Electrolyte Interphase from MOFs for Advanced Zn Metal Anodes

“…Owing to significant safety and environmental concerns, traditional lithium‐ion and sodium‐ion batteries can no longer meet the needs of current rechargeable energy storage devices, [ 1 ] which has attracted considerable attention within the last few years. Meanwhile, water‐based batteries and capacitors are coming into the picture as alternative devices.…”

“…Owing to significant safety and environmental concerns, traditional lithium-ion and sodium-ion batteries can no longer meet the needs of current rechargeable energy storage devices, [1] which has attracted considerable attention within the last few but also produces a dramatic decrease in coulomb efficiency. Even worse, the internal Zn metal remains exposed to the electrolyte, which can also result in further Zn corrosion.…”

Limiting voltage and capacity fade of lithium-rich, low cobalt Li1.2Ni0.13Mn0.54Fe0.1Co0.03O2 by controlling the upper cut-off voltage

“…10,11 LiMn 2 O 4 also suffers from severe capacity fading at high temperatures due to the Jahn-Teller distortion of Mn 3+ , Mn ions' dissolution in electrolyte and the formation of two cubic phases and growth of microstrain. 10,12,13 One of the most common alternatives has been lithium nickel cobalt manganese oxides Li(NiMnCo)O 2 (NMC) due to their relative low cost, high capacity, and better thermal stability. 14 However, Li(NiMnCo)O 2 has inherent disadvantages such as cation mixing, toxicity and high-capacity losses in the rst discharge cycles.…”