Improvement of electrochemical properties of the spinel LiMn2O4 using a Cr dopant effect

Wang, Guoxiu; Bradhurst, D. H.; Liu, Huan; Dou, Shi Xue

doi:10.1016/s0167-2738(98)00554-2

Cited by 91 publications

(58 citation statements)

References 15 publications

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“…8b and 9. The impedance spectra of the LiMn 2 O 4 are similar to those observed by others, 18,22,38,43 which reflects the Li ion migration through the surface film (high-to-medium frequency semicircle; 0.35 MHz-8 kHz), charge transfer at the interface coupled with the double layer capacitance (medium frequency; 8 kHz-10 Hz) and a Warburg contribution that reflects Li ion migration through the bulk of the material (0.2 Hz-3 mHz). The third semicircle at the low frequency side (10 Hz-0.2 Hz) , which is pronounced only in doped spinels was not, however, seen by others.…”

Section: Eissupporting

confidence: 86%

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Li ion kinetic studies on spinel cathodes, Li(M1/6Mn11/6)O4 (M = Mn, Co, CoAl) by GITT and EIS

2002

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Pristine and substituted spinels, Li(M 1/6 Mn 11/6 )O 4 (M~Co 1/6 , Co 1/12 Al 1/12 ) were prepared and their cathodic performance up to 80 cycles at ambient temperature and at 50 uC and the Li ion kinetic parameters obtained by galvanostatic intermittent titration technique (GITT) at ambient temperature and 50 uC and electrochemical impedance spectroscopy (EIS) at ambient temperature up to 80 cycles were compared to understand the improved performance observed for the doped spinels. The apparent Li diffusion coefficient (D Li ) obtained from GITT in the voltage range of operation of the cell (3.5-4.3 V vs. Li) at ambient temperature and 50 uC is in the range 1 6 10 29 -10 210 cm 2 s 21 for M~Mn, Co and (Co,Al). The D Li vs. voltage plots show indication of suppression of two-phase formation in doped spinels. Distinct changes in the EIS-derived parameters and the D Li values in the compounds with M~Co, (Co,Al) as compared to LiMn 2 O 4 lead to the conclusion that the observed cycling stability in the doped spinels is contributed by the Li ion kinetics in addition to the suppression of the structural changes and associated material dissolution.

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Section: Eissupporting

confidence: 86%

“…The third semicircle at the low frequency side (10 Hz-0.2 Hz) , which is pronounced only in doped spinels was not, however, seen by others. 18,22,43 Fitting the experimental data points with the equivalent circuit (Fig. 8b) gives R 3~1 0(¡2) V for MC oAl after its first charge.…”

Section: Eismentioning

confidence: 99%

Li ion kinetic studies on spinel cathodes, Li(M1/6Mn11/6)O4 (M = Mn, Co, CoAl) by GITT and EIS

2002

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“…34,35 Anion substitutions were also reported in the literature and are used to counteract the capacity reduction caused by cation substitutions, as first reported by Amatucci et al for F-substituted spinel structures (LiMn 2-y M y O 4-z F z ). 7 Elemental substitutions in the LMO lattice can prevent the Mn dissolution to some extent.…”

Section: A6316mentioning

confidence: 92%

“…For example, the Mn dissolution rate from LMO is greater at high potentials (above 4 V vs. Li/Li + ) than at lower potentials (below 4 V vs. Li/Li + ), a fact which is inconsistent with the disproportionation concept, since the fraction of Mn 4+ cations in the LMO lattice increases with increasing potential. 13,17 While a very large number of studies in the literature report a variety of results on the oxidation state of Mn species in the negative or positive electrodes of cycled LMO-graphite cells, 11,[18][19][20][21] Mitigation measures for Mn dissolution.-Several mitigation measures for the dissolution of Mn ions and its consequences were proposed in the literature over the past two decades: electrolyte optimization by a judicious choice of additives; [26][27][28][29][30][31][32][33] elemental substitutions in the LMO lattice, 7,13,17,34,35 in order to increase the average oxidation state of the Mn ions; surface coatings on the active material powder or electrodes, in order to avoid direct contacts between electrode and electrolyte solution, and thus prevent HF and other acid attack on the active material; [36][37][38][39][40][41][42] chemically active binders; [43][44][45][46][47][48][49][50] an inorganic Mn ions scavenging barrier layer such as lithium titanate 51 or a solid Li-ion conducting and Mn ions blocking membrane 52 placed in the inter-electrode space; and the utilization of chemically activ...…”

Section: A6316mentioning

confidence: 99%

Review—Multifunctional Materials for Enhanced Li-Ion Batteries Durability: A Brief Review of Practical Options

Banerjee

Shilina

Ziv

et al. 2017

J. Electrochem. Soc.

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Transition metal (TM) ions dissolution from positive electrodes, migration to and deposition on negative electrodes, followed by Mn-catalyzed reactions of solvents and anions, with loss of Li + ions, is a major degradation (DMDCR) mechanism in Li-ion batteries (LIBs) with spinel positive electrode materials. While the details of the DMDCR mechanism are still under debate, it is clear that HF and other acid species' attack is the main cause in solutions with LiPF 6 electrolyte. We first review the work on various mitigation measures for the DMDCR mechanism, now spanning more than two decades. We then discuss recent progress on our understanding of Mn species in electrolyte solutions and the extension of a mitigation measure first proposed by Tarascon and coworkers in 1999, namely chelation of TM cations, to Mn cation trapping, HF scavenging, and alkali metal ions dispensing multi-functional materials. We focus on practicable, drop-in technical solutions, based on placing such materials in the inter-electrode space, with significant benefits for LIBs performance: increased capacity retention during operation at room and above-ambient temperatures as well as robust (both maximally ionically conducting and electronically insulating) solid-electrolyte interfaces, having reduced charge transfer and film resistances at both negative and positive electrodes. We illustrate the multifunctional materials approach with both new and previously published data. We also discuss and offer our evaluation regarding the merits and drawbacks of the various mitigation measures, with an eye for practically relevant technical solutions capable to meet both the performance requirements and cost constraints for commercial LIBs, and end with recommendations for future work. Li-ion batteries (LIBs) dominate the global market for energystorage devices nowadays and are used in a variety of applications, ranging from portable consumer electronics, to electrical grid storage, to load-levelling and electrified vehicles.1 Electrified vehicles are the most demanding among all LIBs applications in terms of both duty cycle and durability, since the batteries are subjected to a wide range of temperatures and charging/discharging rates, while customers expect a 10 years lifetime. Incessant research on various positive and negative active materials resulted in several promising electrode materials with various crystal structures and chemistries being developed over the past decades, such as layered (LiCoO 2 , LiNi 1-x-y Co x Al y O 2 , Ni 1-x-y Co x Mn y O 2 ), spinel (LiMn 2 O 4 , a.k.a. LMO; LNi 0.5 Mn 1.5 O 2 , a.k.a. LNMO), and olivine (LiFePO 4, LiVPO 4 ) for positive, as well as graphite, silicon, silicon-oxide, and lithium titanate for negative electrodes.2 New developments in electrode materials notwithstanding, LIBs for automotive transportation still need considerable improvements in terms of both performance and durability. Among transition metal (TM) oxide cathodes, LiMn 2 O 4 spinel would be most suited for automotive power cells due to i...

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“…Two derivatives which have attracted many researchers since the early 90's, LiNi x Mn 2-x O 4 [74], and LiCr x Mn 2-x O 4 [52, 75,76], have demonstrated a remarkable improvement on the cyclability of spinel magnesium oxides.…”

Section: Derivative Compoundsmentioning

confidence: 99%

Review on Synthesis, Characterizations, and Electrochemical Properties of Cathode Materials for Lithium Ion Batteries

Bensalah¹,

Dawood²

2016

J Material Sci Eng

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The development of cutting-edge cathode materials is a challenging research topic aiming to improve the energy and power densities of lithium ion batteries (LIB) to cover the increasing demands for energy storage devices. Therefore, highly needed further improvements in the performance characteristics of Li-ion batteries are largely dependent on our ability to develop novel materials with greatly improved Li ion storage capacities. Three different types of cathode materials including intercalation, alloying and conversion materials are reviewed in this paper in order to orientate our researches towards highly performant LIBs batteries. This includes characteristics of different cathode materials and approaches for improving their performances.

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Improvement of electrochemical properties of the spinel LiMn2O4 using a Cr dopant effect

Cited by 91 publications

References 15 publications

Li ion kinetic studies on spinel cathodes, Li(M1/6Mn11/6)O4 (M = Mn, Co, CoAl) by GITT and EIS

Li ion kinetic studies on spinel cathodes, Li(M1/6Mn11/6)O4 (M = Mn, Co, CoAl) by GITT and EIS

Review—Multifunctional Materials for Enhanced Li-Ion Batteries Durability: A Brief Review of Practical Options

Review on Synthesis, Characterizations, and Electrochemical Properties of Cathode Materials for Lithium Ion Batteries

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