Solid State Synthesis and Properties of Doped LiMnO<sub>2</sub> Cathode Materials

Ammundsen, Brett; Desilvestro, Johann; Groutso, Tania; Hassell, David; Metson, James B.; Regan, Ed; Steiner, Rudolf; Pickering, Paul J.

doi:10.1557/proc-575-49

Cited by 6 publications

(4 citation statements)

References 12 publications

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“…This similarity suggests a way to analyze the relative tendency of different dopants to destabilize the monoclinic distortion. With sufficient doping, the orthorhombic structure would also likely transform to rhombohedral [26].…”

Section: Structurementioning

confidence: 99%

Phase stability of cation-doped LiMnO₂within the GGA+U approximation

Shukla

Prasad

et al. 2008

Modelling Simul. Mater. Sci. Eng.

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First principles density functional theory calculations within the GGA+U approximation were performed for LiMn 1−x M x O 2 , a candidate cathode material for lithium-ion batteries, with (x = 0.25, M=Ni, Fe, Co, Mg), to investigate the effect of doping on the destabilization of the monoclinic structure relative to the layered rhombohedral structure. A primary motivation of this work was to determine to what extent the predictions of the electronically more realistic GGA+U treatment would differ from those obtained within the GGA. Several significant qualitative changes are found. For the pristine system in the rhombohedral structure, Mn ions show a high-spin state within GGA+U, rather than the low spin (metallic) state found in GGA. The doped rhombohedral structure is unstable within GGA+U, rather than metastable, as in GGA. In the monoclinic structure, the dopant oxidation states are the same (trivalent Fe, divalent Co, Ni) in GGA+U and GGA. Co and Ni ions show a higher spin state in GGA+U than in GGA. The divalent dopants destabilized the monoclinic structure to a greater extent than trivalent dopants within the GGA+U, as expected from previous GGA calculations. Overall, our results suggest that the relatively close agreement sometimes found between properties calculated within the GGA and GGA+U may be misleading, because the underlying electronic behaviors may be profoundly different.

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Section: Structurementioning

confidence: 99%

Phase stability of cation-doped LiMnO₂within the GGA+U approximation

Shukla

Prasad

et al. 2008

Modelling Simul. Mater. Sci. Eng.

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“…To characterize the valence state of Mn in bulk, Figure a shows the Mn 2p 3/2 XPS spectrum of M-LCO, which was collected after 10 min of etching. The center of the peak is positioned at 642.1 eV, indicating that Mn 3+ ions exist in the interior of LCO. − This result could ascribe to the diffusion of Mn during high-temperature heating of the modification. For further verification, Figure b shows the STEM–EDS point analyses of an M-LCO sample that was treated by focused ion beam (FIB) fabrication.…”

Section: Resultsmentioning

confidence: 97%

One-Step Integrated Comodification to Improve the Electrochemical Performances of High-Voltage LiCoO₂ for Lithium-Ion Batteries

Qian

Lyu

et al. 2020

ACS Sustainable Chem. Eng.

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While the theoretical capacity of LiCoO 2 is as high as 274 mA h g −1 , its practical specific capacity is only about 140 mA h g −1 when it was first applied in lithium-ion batteries. Raising the charging cutoff voltage can effectively enhance the specific capacity of LiCoO 2 . For example, when increasing the cutoff voltage to 4.5 V vs Li + /Li, the specific capacity will increase to 185 mA h g −1 . However, the surface and structure instability of LiCoO 2 under high-voltage operation lead to rapid capacity decay. Various modified strategies have been proposed, such as element doping and surface coating. In this work, we develop a one-step integrated comodification approach to achieve a long cycle life of LiCoO 2 in the range of 3.0−4.5 V. The phosphate surface layer suppresses the side reaction of electrolyte and Co dissolution. Mn doping enhances the structure stability of LiCoO 2 . The capacity retention of a modified LiCoO 2 with a cutoff voltage of 4.5 V is as high as 83.7% even after 700 cycles.

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“…Layered oxide materials are readily obtained from well-established, pioneering methods such as solid-state reactions, [57,58] hydrothermal syntheses, [59,60] coprecipitation procedures, [61,62] and the sol-gel method. [63,64] Solid-state synthesis routes avoid complex, multistep procedures and take advantage of easily obtained and relatively cheap carbonate and precursors while permitting the inclusion of dopants and phase variations by adjusting each precursor's stoichiometric amounts.…”

Section: Synthesis Methodsmentioning

confidence: 99%

Electrochemical Overview: A Summary of ACo_xMn_yNi_zO₂ and Metal Oxides as Versatile Cathode Materials for Metal‐Ion Batteries

Pimlott

Street

Down

et al. 2021

Adv Funct Materials

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Early LiCoO 2 research provided the basis for the tremendous commercial success of Li + batteries since their invention in the early 1990s. Today, LiN-iMnCoO 2 (Li-NMC) is one of the most widely used batteries in the rapidly evolving electronic vehicle industry. Li-NMC batteries continue to receive significant interest as research efforts aim to partially, or entirely, replace the use of scarcely available and toxic Co with elemental doping to form binary, ternary, and quaternary layered oxides. Furthermore, safety concerns and rising uncertainty for the future of Li supplies have resulted in growing curiosity toward non-Li + rechargeable batteries such as Na + and K + . Unfortunately, the success of Li + host materials does not always directly transfer to Na + and K + batteries due to the difficulty of reversibly intercalating larger ions without irreparably distorting the host structure. Consequently, this report provides an overview of the Li-based materials surrounding the success of commercial Li-NMC and the subsequent progress of their lesser studied Na and K counterparts. The challenges for current cathode materials are highlighted, and the opportunities for progression are suggested. The summary presented in this review can be consulted to steer new and unique research avenues for layered oxide materials as metal-ion battery cathodes.

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Solid State Synthesis and Properties of Doped LiMnO₂ Cathode Materials

Cited by 6 publications

References 12 publications

Phase stability of cation-doped LiMnO₂within the GGA+U approximation

Phase stability of cation-doped LiMnO₂within the GGA+U approximation

One-Step Integrated Comodification to Improve the Electrochemical Performances of High-Voltage LiCoO₂ for Lithium-Ion Batteries

Electrochemical Overview: A Summary of ACo_xMn_yNi_zO₂ and Metal Oxides as Versatile Cathode Materials for Metal‐Ion Batteries

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Solid State Synthesis and Properties of Doped LiMnO2 Cathode Materials

Cited by 6 publications

References 12 publications

Phase stability of cation-doped LiMnO2within the GGA+U approximation

Phase stability of cation-doped LiMnO2within the GGA+U approximation

One-Step Integrated Comodification to Improve the Electrochemical Performances of High-Voltage LiCoO2 for Lithium-Ion Batteries

Electrochemical Overview: A Summary of ACoxMnyNizO2 and Metal Oxides as Versatile Cathode Materials for Metal‐Ion Batteries

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Solid State Synthesis and Properties of Doped LiMnO₂ Cathode Materials

Phase stability of cation-doped LiMnO₂within the GGA+U approximation

Phase stability of cation-doped LiMnO₂within the GGA+U approximation

One-Step Integrated Comodification to Improve the Electrochemical Performances of High-Voltage LiCoO₂ for Lithium-Ion Batteries

Electrochemical Overview: A Summary of ACo_xMn_yNi_zO₂ and Metal Oxides as Versatile Cathode Materials for Metal‐Ion Batteries