A comparative study on electrochemical cycling stability of lithium rich layered cathode materials Li 1.2 Ni 0.13 M 0.13 Mn 0.54 O 2 where M = Fe or Co

Laisa, C.P.; Kumar, Ashwani; Chandrasekaran, S. Selva; Murugan, P.; Lakshminarasimhan, N.; Govindaraj, R.; Ramesha, K.

doi:10.1016/j.jpowsour.2016.05.107

Cited by 63 publications

(50 citation statements)

References 51 publications

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“…For the as‐prepared material, the Ni 2p spectra exhibited an asymmetric peak at 854.1 eV, which was assigned to Ni 2+ . After it was charged to 4.8 V, the Ni 2p 3/2 peak shifted to a higher binding energy of 859.5 eV, which implied the oxidation of Ni 2+ to Ni 4+ . After it was discharged to 2.0 V, Ni 2+ and Ni 3+ (binding energy at 857.2) were detected.…”

Section: Resultsmentioning

confidence: 95%

“…In the second cycle, a pair of symmetric peaks can be clearly seen at 4.2 V for the oxidation and 3.8 V for reduction. These redox peaks were assigned to the redox reaction of Fe 3+ /Fe 4+ and Ni 2+ /Ni 3+ , which contributed most of the capacity. Furthermore, a pair of small peaks were observed at approximately 3.25 V, which were assigned to the redox of the Mn 3+ /Mn 4+ couples, although the amount of Mn 3+ was small.…”

Section: Resultsmentioning

confidence: 99%

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A Cobalt‐Free Li(Li_0.16Ni_0.19Fe_0.18Mn_0.46)O₂ Cathode for Lithium‐Ion Batteries with Anionic Redox Reactions

Wei

Hao

et al. 2019

ChemSusChem

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Lithium‐rich, Mn‐based layered oxides Li2MnO3‐LiMO2 (M=Ni, Co) have been considered as promising cathode candidates owing to their high capacity. However, the resources shortage and high price of cobalt make it imperious to substitute cobalt with other high‐abundance elements. Here, we synthesized a low‐cost, cobalt‐free, Fe‐substituted oxide material, Li(Li0.16Ni0.19Fe0.18Mn0.46)O2. It exhibited a high reversible capacity of 169.2 mAh g−1 after 100 cycles and maintained an extraordinarily high discharge potential during cycling. X‐ray photoelectron spectroscopy and DFT calculations revealed that super iron FeIV exists in the delithiated state, and oxygen participates in the redox reaction in addition to the Ni2+/Ni4+ and Fe3+/Fe4+ redox couples. The anionic oxidation preferentially occurred on oxygen with a Li−O−Li configuration and with oxidized Fe and Ni coordination.

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Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

A Cobalt‐Free Li(Li_0.16Ni_0.19Fe_0.18Mn_0.46)O₂ Cathode for Lithium‐Ion Batteries with Anionic Redox Reactions

Wei

Hao

et al. 2019

ChemSusChem

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“…This leads to a less pronounced crystal structure transformation in ILE than LP30. [8,49] The m/z = 44 and 22 signals appearing during cycling in LP30 are assigned to CO 2 . The m/z = 28 signal also present in this measurement may derive from CO or C 2 H 4 formation.…”

Section: Identifying the Origin Of The Improved Cycling Stability Of mentioning

confidence: 99%

Reducing Capacity and Voltage Decay of Co‐Free Li_1.2Ni_0.2Mn_0.6O₂ as Positive Electrode Material for Lithium Batteries Employing an Ionic Liquid‐Based Electrolyte

Kim

Diemant

et al. 2020

Advanced Energy Materials

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Lithium‐rich layered oxides (LRLOs) exhibit specific capacities above 250 mAh g−1, i.e., higher than any of the commercially employed lithium‐ion‐positive electrode materials. Such high capacities result in high specific energies, meeting the tough requirements for electric vehicle applications. However, LRLOs generally suffer from severe capacity and voltage fading, originating from undesired structural transformations during cycling. Herein, the eco‐friendly, cobalt‐free Li1.2Ni0.2Mn0.6O2 (LRNM), offering a specific energy above 800 Wh kg−1 at 0.1 C, is investigated in combination with a lithium metal anode and a room temperature ionic liquid‐based electrolyte, i.e., lithium bis(trifluoromethanesulfonyl)imide and N‐butyl‐N‐methylpyrrolidinium bis(fluorosulfonyl)imide. As evidenced by electrochemical performance and high‐resolution transmission electron microscopy, X‐ray photoelectron spectroscopy, and online differential electrochemical mass spectrometry characterization, this electrolyte is capable of suppressing the structural transformation of the positive electrode material, resulting in enhanced cycling stability compared to conventional carbonate‐based electrolytes. Practically, the capacity and voltage fading are significantly limited to only 19% and 3% (i.e., lower than 0.2 mV per cycle), respectively, after 500 cycles. Finally, the beneficial effect of the ionic liquid‐based electrolyte is validated in lithium‐ion cells employing LRNM and Li4Ti5O12. These cells achieve a promising capacity retention of 80% after 500 cycles at 1 C.

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“…Fe-substituted Li-rich materials [26][27][28][29][30][31][32] have attracted great interesti nr ecent years. [38][39][40][41][42] Therefore, ac lear pictureo ft he redox mechanism of TM or Oo ft he Fe-substituted Li-rich system is necessary to understand whether the behavior of Fe is like that of Co, in which Oi ons are oxidized, and the functionofFes ubstitution. [34,35] In Fe-substitutedL i-rich materials, like other Li-rich materials, anionic reversible redox reactionO 2À /O 2 2À was detected, [36,37] but whether Fe 3 + participates in the redox reaction or not during charging/discharging remains unsure.…”

Section: Introductionmentioning

confidence: 99%

“…[34,35] In Fe-substitutedL i-rich materials, like other Li-rich materials, anionic reversible redox reactionO 2À /O 2 2À was detected, [36,37] but whether Fe 3 + participates in the redox reaction or not during charging/discharging remains unsure. [38][39][40][41][42] Therefore, ac lear pictureo ft he redox mechanism of TM or Oo ft he Fe-substituted Li-rich system is necessary to understand whether the behavior of Fe is like that of Co, in which Oi ons are oxidized, and the functionofFes ubstitution.…”

Section: Introductionmentioning

confidence: 99%

A Cobalt‐Free Li(Li_0.17Ni_0.17Fe_0.17Mn_0.49)O₂ Cathode with More Oxygen‐Involving Charge Compensation for Lithium‐Ion Batteries

et al. 2019

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High‐energy‐density and low‐cost lithium‐ion batteries are sought to meet increasing demand for portable electronics. In this study, a cobalt‐free Li(Li0.17Ni0.17Fe0.17Mn0.49)O2 (LNFMO) cathode material is chosen, owing to the reversible anionic redox couple O2−/O−. The aim is to elucidate the Fe‐substitution function and oxygen redox mechanism of experimentally synthesized Li(Li0.16Ni0.19Fe0.18Mn0.46)O2 by DFT. The redox processes of cobalt‐containing Li(Li0.17Ni0.17Co0.17Mn0.49)O2 (LNCMO) are compared with those of LNFMO. Redox couples including Ni2+/Ni3+/Ni4+, Fe3+/Fe4+ or Co3+/Co4+, and O2−/O− are found, confirmed by a X‐ray photoelectron spectroscopy, and explained by redox competition between O and transition metals. In LNFMO and LNCMO, O ions with an Li‐O‐Li configuration readily participate in oxidation, and the most active O ions are coordinated to Mn4+ and Li+. Oxidation of O in LNCMO is triggered earlier, along with that of Co. Fe substitution activates O ions, contributes additional oxygen redox charge compensation of 0.44 e per formula unit, avoids concentrated accumulation of oxygen oxidation, and improves structural stability. This work provides new scope for designing cobalt‐free, low‐cost, and higher‐energy‐density cathode materials for Li‐ion batteries.

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A comparative study on electrochemical cycling stability of lithium rich layered cathode materials Li 1.2 Ni 0.13 M 0.13 Mn 0.54 O 2 where M = Fe or Co

Cited by 63 publications

References 51 publications

A Cobalt‐Free Li(Li_0.16Ni_0.19Fe_0.18Mn_0.46)O₂ Cathode for Lithium‐Ion Batteries with Anionic Redox Reactions

A Cobalt‐Free Li(Li_0.16Ni_0.19Fe_0.18Mn_0.46)O₂ Cathode for Lithium‐Ion Batteries with Anionic Redox Reactions

Reducing Capacity and Voltage Decay of Co‐Free Li_1.2Ni_0.2Mn_0.6O₂ as Positive Electrode Material for Lithium Batteries Employing an Ionic Liquid‐Based Electrolyte

A Cobalt‐Free Li(Li_0.17Ni_0.17Fe_0.17Mn_0.49)O₂ Cathode with More Oxygen‐Involving Charge Compensation for Lithium‐Ion Batteries

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A comparative study on electrochemical cycling stability of lithium rich layered cathode materials Li 1.2 Ni 0.13 M 0.13 Mn 0.54 O 2 where M = Fe or Co

Cited by 63 publications

References 51 publications

A Cobalt‐Free Li(Li0.16Ni0.19Fe0.18Mn0.46)O2 Cathode for Lithium‐Ion Batteries with Anionic Redox Reactions

A Cobalt‐Free Li(Li0.16Ni0.19Fe0.18Mn0.46)O2 Cathode for Lithium‐Ion Batteries with Anionic Redox Reactions

Reducing Capacity and Voltage Decay of Co‐Free Li1.2Ni0.2Mn0.6O2 as Positive Electrode Material for Lithium Batteries Employing an Ionic Liquid‐Based Electrolyte

A Cobalt‐Free Li(Li0.17Ni0.17Fe0.17Mn0.49)O2 Cathode with More Oxygen‐Involving Charge Compensation for Lithium‐Ion Batteries

Contact Info

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A Cobalt‐Free Li(Li_0.16Ni_0.19Fe_0.18Mn_0.46)O₂ Cathode for Lithium‐Ion Batteries with Anionic Redox Reactions

A Cobalt‐Free Li(Li_0.16Ni_0.19Fe_0.18Mn_0.46)O₂ Cathode for Lithium‐Ion Batteries with Anionic Redox Reactions

Reducing Capacity and Voltage Decay of Co‐Free Li_1.2Ni_0.2Mn_0.6O₂ as Positive Electrode Material for Lithium Batteries Employing an Ionic Liquid‐Based Electrolyte

A Cobalt‐Free Li(Li_0.17Ni_0.17Fe_0.17Mn_0.49)O₂ Cathode with More Oxygen‐Involving Charge Compensation for Lithium‐Ion Batteries