Improved lithium manganese oxide spinel/graphite Li-ion cells for high-power applications

Amine, K.; Liu, J; Sun, Kai; Belharouak, Ilias; Hyung, Yoo Eup; Vissers, D.R.; Henriksen, G. L.

doi:10.1016/j.jpowsour.2003.11.007

Cited by 264 publications

(252 citation statements)

References 9 publications

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“…to capacity fading especially at elevated temperatures.D issolution of Mn into the electrolyte [20][21][22] and Jahn-Teller distortions causingf ailure of structural integrity [21,23] are discussed as possible reasons,but the underlying mechanisms of capacity fadinga re not yet clear. LNMO operates at ah igher potential of 4.7 Vv ersus Li/Li + ,a nd it thus offers ah igher energy density and is ap romising candidate for high-voltage Li-ion batteries.O wing to strong doping with Ni, LNMOh as enhanced structural integrity and capacity retentionwhile cycling relative to LiMn 2 O 4 .…”

Section: Introductionmentioning

confidence: 99%

Three‐Dimensional Microstructural Characterization of Lithium Manganese Oxide with Atom Probe Tomography

et al. 2016

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The microstructure of the active material of Li‐ion batteries has a crucial influence on local ion‐transport processes but is not yet well characterized. Atom probe tomography (APT), a method combining sub‐nanometer spatial resolution with sub‐parts‐per‐thousand chemical resolution is well suited for 3 D microstructural characterization. Herein, the results of the characterization of lithium (nickel)manganese oxides [L(N)MO] with APT are presented. Structural and chemical defects of different dimensions such as the segregation of Na impurities to grain boundaries and the appearance of a Ni‐rich foreign phase are detected. Furthermore, a lamellar microstructure correlated to fluctuations in the local Li content was observed, and its influence on Li transport in the material is discussed. In defect‐free regions, the lattice planes of LMO are reconstructed for the first time, and the high spatial resolution of APT is revealed. Thus, the results demonstrate the potential of APT for the 3 D microstructural characterization of LMO.

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Section: Introductionmentioning

confidence: 99%

Three‐Dimensional Microstructural Characterization of Lithium Manganese Oxide with Atom Probe Tomography

et al. 2016

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“…9 Remedies have been implemented to mitigate the effects of acid attack in lithium-ion batteries. 3,[10][11][12] Little theoretical analysis has been performed, however, to gain a more fundamental understanding of the reactions or as a tool to screen materials for their acidattack-resistant qualities. Most desirable, in principle, would be the calculation of absolute reaction rates, which are controlled to a large extent by kinetic factors.…”

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confidence: 99%

Free Energies for Acid Attack Reactions of Lithium Cobaltate

Benedek¹,

Walle²

2008

J. Electrochem. Soc.

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The attack of lithium-ion battery cathodes by stray aqueous HF, with resultant dissolution, protonation, and possibly other unintended reactions, can be a significant source of capacity fade. We explore the calculation of reaction free energies of lithium cobaltate in acid by a "hybrid" method, in which solid-phase free energies are calculated from first principles at the generalized gradient approximation + intrasite coulomb interaction ͑GGA + U͒ level and tabulated values of ionization potentials and hydration energies are employed for the aqueous species. Analysis of the dissolution of the binary oxides Li 2 O and CoO suggests that the atomic energies for Co and Li should be shifted from values calculated by first principles to yield accurate reaction free energies within the hybrid method. With the shifted atomic energies, the hybrid method was applied to analyze proton-promoted dissolution and protonation reactions of LiCoO 2 in aqueous acid. Reaction free energies for the dissolution reaction, the reaction to form Co 3 O 4 spinel, and the proton-for-lithium exchange reaction are obtained and compared to empirical values. An extension of the present treatment to consider partial reactions is proposed, with a view to investigating interfacial and environmental effects on the dissolution reaction. Stray water in lithium-ion batteries reacts with organic electrolytes to generate HF 1,2 which attacks the cathode material and causes irreversible capacity losses.3-5 Most of the families of cathode materials of greatest current interest, including spinel and layered systems, dissolve in acid, with Li-Mn spinel, LiMn 2 O 4 , showing the highest dissolution rate.3 Acid-promoted reactions can also be beneficial, e.g., in the processing of composite cathode materials 6-8 and to leach spent cathode materials for metal recycling. Remedies have been implemented to mitigate the effects of acid attack in lithium-ion batteries.3,10-12 Little theoretical analysis has been performed, however, to gain a more fundamental understanding of the reactions or as a tool to screen materials for their acidattack-resistant qualities. Most desirable, in principle, would be the calculation of absolute reaction rates, which are controlled to a large extent by kinetic factors. Unfortunately, despite a long history of kinetic models, 13 the prediction of oxide dissolution rates from first principles 14 is still a distant prospect. The premise of this work is that the reaction free energy ⌬G r , which is more accessible to computation, 15 may still provide useful guidance, even though it does not enable the prediction of dissolution rates.Accurate calculations of ⌬G r are readily done for reactions for which empirically derived free energies for each reaction species are available. The National Institute of Standards and Technology-Joint Army-Navy-Air Force compilation of formation free energies for ions in aqueous solution and for solid compounds, 16 for example, is convenient for this purpose. Formation free energies for several of the mult...

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“…A variety of strategies have been taken to improve cycling capability of LiMn 2 O 4 based electrodes such as doping [4][5][6][7], surface coating [8][9][10][11][12][13] and functional additives in the electrolyte [1,[14][15][16][17][18][19] at elevated temperatures [20,21]. Ionic liquid-based electrolyte and single-ion-conducting nanocomposite polymer electrolytes are also very promising candidates to solve the LiMn 2 O 4 cycling problems [22][23][24].…”

Section: Introductionmentioning

confidence: 99%

“…The molecular configuration was helpful to delocalize the negative charge of the central ion, and the anion became more thermodynamically stable. Moreover, it was reported that the cell using LiBOB-based electrolyte maintained stable performance at elevated temperature due to excellent thermal stability and absence of HF [20,21]. Recently we reported a novel kind of "main-chain" type polymeric lithium tartaric acid borate, which possessed a high thermal decomposition temperature at 330 • C. It was verified that the ethylene carbonate/dimethyl carbonate (EC/DMC) swollen polymeric lithium tartaric acid borate @ poly(vinylidene fluorideco-hexafluoropropylene (PLTB@PVDF-HFP) exhibited a superior ionic conductivity at room temperature ( = 0.50 mS cm −1 ) and significantly high lithium ion transference number (t Li+ = 0.91) [26].…”

Section: Introductionmentioning

confidence: 99%

A single-ion gel polymer electrolyte system for improving cycle performance of LiMn2O4 battery at elevated temperatures

Qin

Liu

Ding

et al. 2014

Electrochimica Acta

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a b s t r a c tThe LiMn 2 O 4 based lithium batteries using commercially available electrolytes suffer from poor cycling performance at elevated temperatures (above 55• C). This is mainly caused by the Mn dissolution generated from HF thermally decomposed from the LiPF 6 salt at elevated temperatures. In this paper, a single-ion gel polymer electrolyte (polymeric lithium tartaric acid borate @ poly(vinylidene fluoride-cohexafluoropropylene) was explored for improving the cycling performance of the LiMn 2 O 4 based lithium battery at elevated temperatures owing to superior thermal stability and comparable ionic conductivity. It was manifested that the Li/LiMn 2 O 4 cells using this single-ion gel polymer electrolyte showed stable charge/discharge voltage profiles, preferable rate capability and excellent cycling performance both at room temperature and elevated temperature of 55• C. The dissolution of metallic Mn in this electrolyte is significantly suppressed than that of LiPF 6 electrolyte. These superior performances could endow this single-ion gel polymer electrolyte a promising alternative to the conventional liquid electrolyte system in the LiMn 2 O 4 battery at elevated temperatures.

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Improved lithium manganese oxide spinel/graphite Li-ion cells for high-power applications

Cited by 264 publications

References 9 publications

Three‐Dimensional Microstructural Characterization of Lithium Manganese Oxide with Atom Probe Tomography

Three‐Dimensional Microstructural Characterization of Lithium Manganese Oxide with Atom Probe Tomography

Free Energies for Acid Attack Reactions of Lithium Cobaltate

A single-ion gel polymer electrolyte system for improving cycle performance of LiMn2O4 battery at elevated temperatures

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