High energy density layered-spinel hybrid cathodes for lithium ion rechargeable batteries

Basu, Suddhasatwa; Dahiya, P. P.; Akhtar, Mainul; Ray, S. K.; Chang, Jeng‐Kuei; Majumder, S. B.

doi:10.1016/j.mseb.2016.04.008

Cited by 9 publications

(10 citation statements)

References 27 publications

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“…The peak corresponding to this process and the associated reduction of Mn 4+ to Mn 3+ is observed below 3.5 V in the cathodic process. 35,36 The CV curves also indicate that no oxidation peak is observed below 3.5 V during the initial charging process, and this confirms that the oxidation state of manganese is +4 in the as-synthesized NMO. From the second cycle onward, there is a slight shift in the oxidation peak at 4.1 V toward the lower voltage region (∼3.84 V) and the oxidation peak above 4.5 V in the initial charging process disappears.…”

Section: Electrochemical Performancesupporting

confidence: 57%

“…The oxidation and reduction peaks observed at 4.32 and 4.24 V is attributed to the deinsertion/insertion of the Li + ion, respectively, at vacant 8a tetrahedral sites of the spinel structure formed by MnO 2 . 35,39 The oxidation and reduction peaks at 3.28 and 3.24 V (low scan rate CV (25 μVs −1 ) shown in Figure 9b) is attributed to the deinsertion/insertion of lithium ion, respectively, at 16c octahedral sites of the spinel structure. 35,39 Furthermore, the second and third cycles almost overlap, which demonstrates the reversibility of the NMO material.…”

Section: Electrochemical Performancementioning

confidence: 98%

“…35,39 The oxidation and reduction peaks at 3.28 and 3.24 V (low scan rate CV (25 μVs −1 ) shown in Figure 9b) is attributed to the deinsertion/insertion of lithium ion, respectively, at 16c octahedral sites of the spinel structure. 35,39 Furthermore, the second and third cycles almost overlap, which demonstrates the reversibility of the NMO material. The electrochemical reactions taking place in the voltage window of 2.0−4.8 V are given below:…”

Section: Electrochemical Performancementioning

confidence: 98%

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Synthesis and Electrochemical Characterization of a Li-Rich Li_1.17Ni_0.34Mn_0.5O₂Cathode Material for Lithium-Ion Cells

et al. 2022

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Lithium-rich layered cathodes have emerged as fascinating materials for high energy density lithium-ion cells owing to their high working voltage window and specific capacity. Herein, we report a novel high-capacity Lirich cathode material having the composition Li 1.17 Ni 0.34 Mn 0.5 O 2 synthesized through a simple carbonate co-precipitation method without using any chelating agents. Inductively coupled plasma atomic emission spectroscopy (ICP-AES), Xray diffraction (XRD), and field emission scanning electron microscopy (FE-SEM) coupled with energy-dispersive spectroscopy (EDS) were employed to characterize the chemical composition, structure, morphology, and elemental distribution, respectively of the synthesized cathode material. The XRD results revealed a well-defined layered structure, and the SEM images show a porous structure, which is beneficial for electrolyte infiltration and easy lithium-ion diffusion. The material delivered an initial discharge capacity of 250.3 mAhg −1 at C/10 rate and exhibited excellent cycling stability (capacity retentions of >98% at C/10 and >90% at 1C rates at the end of 100 and 200 cycles, respectively). Rate capability studies show that the material delivers discharge capacities of 242.3 mAhg −1 at C/5, 220.1 mAhg −1 at C/2, 183.7 mAhg −1 at 1C, and 131.5 mAhg −1 at 2C rates. The excellent electrochemical performance of this cobalt-free high capacity Li-rich cathode material makes it a promising candidate for high energy density lithium-ion cells.

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Section: Electrochemical Performancesupporting

confidence: 57%

Section: Electrochemical Performancementioning

confidence: 98%

Section: Electrochemical Performancementioning

confidence: 98%

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Synthesis and Electrochemical Characterization of a Li-Rich Li_1.17Ni_0.34Mn_0.5O₂Cathode Material for Lithium-Ion Cells

et al. 2022

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“…Surprisingly, a similar behavior has been observed in the orthorhombic form of Li 2 MnSiO 4 as well, but its origin is still under investigation. 21,22 Likewise, an unidentified pair of peaks almost at the same potential has been noted in spinel LiMn 2 O 4 whose origin has been explained by a phase transition from the cubic to tetragonal phase induced by the Jahn−Teller distortion effect of the Mn 3+ ion. 23,24 In a similar way, the appearance of an additional pair of peaks at a lower voltage could be explained by the structural transformation induced by Mn 3+ produced during intercalation of Li + into m-Li 2 MnSiO 4 as evident from the change in the crystalline structure exemplified in the ex situ XRD diffractogram and SAED images recorded at different stages of lithiation/delithiation.…”

Section: Resultsmentioning

confidence: 69%

Facile Electrochemical Activity of Monoclinic Li₂MnSiO₄as Potential Cathode for Li-Ion Batteries

Kesavan¹,

Michael²,

Prabaharan

2019

ACS Appl. Mater. Interfaces

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Synthesis of pure single-phase Li2MnSiO4 is challenging because of its rich polymorphism. Here, we demonstrate our success in preparing crystalline pure, battery-grade monoclinic phase Li2MnSiO4 (LMS) employing the temperature-programmed reaction technique. Systematic analysis of the electrochemical behavior of Li2MnSiO4 reveals its excellent battery activity in the monoclinic phase, with an initial discharge capacity of ∼250 mAh g–1 associated with the reversible intercalation of more than one Li+. The extraction of Li+ ions from Li2MnSiO4 corresponding to the oxidation of Mn2+ to Mn3+ then to Mn4+ appears as single oxidation/reduction peaks at 4.3/3.9 V in the first charge/discharge sweep of cyclic voltammogram within the potential window of 3.0–4.4 V. However, an extension of cathodic sweep to 2.5 V results in the appearance of an additional redox peak at 2.7/3.1 V vs Li+/Lio due to the reversible phase transition of monoclinic phase into battery-active orthorhombic phase induced by Jahn–Teller-active Mn3+ as evident from ex situ X-ray diffractograms. Indeed, the reversible intercalation of Li+ into the newly formed phase accounts for the high specific capacity of LMS within the potential window of 2.5–4.4 V. The capacity loss in the repeated cycles of monoclinic Li2MnSiO4 is explained by the formation of Mn2O3 owing to the dissolution of Mn3+.

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“…In addition to the application to optical materials as mentioned earlier, some compounds such as ramsdellite‐MnO 2 and Li 2 MnO 3 have been applied to cathode materials for Li‐ion batteries. [ 11–13 ] LaMnO 3 , [ 14 ] δ‐MnO 2 , [ 15 ] and LaMn 3 Co 2 Mn 2 O 12 [ 16 ] have also high potential as catalysts and magnetic materials. Based on these backgrounds, therefore, it is important to study and deepen insights related to the properties of Mn 4+ ‐containing materials.…”

Section: Introductionmentioning

confidence: 99%

Novel Findings on the Optical Properties of Mn⁴⁺‐Doped (Rb,K)₂Ge₄O₉ Phosphors

Oka

Nishi

Hayakawa

2022

Physica Status Solidi (b)

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Herein, Mn4+‐doped alkaline‐germanate phosphors are synthesized by using starting chemicals of alkaline (K, Rb) carbonates, GeO2 and MnO2. The compounds exhibit bright red photoluminescence (PL) under ultraviolet and blue excitation. X‐ray diffraction (XRD) and Raman investigation show the formation of solid solutions of trigonal KxRb2−xGe4O9. The potassium content dependence of the red PL shows the intensity maximized at x = 0.5 and 1.5. This behavior is well matched with the absorption of Mn4+ ions. PL quantum efficiencies (QEs) are also estimated and compared with a previous result for germanates synthesized with Mn carbonates as a starting material. The radiative and nonradiative transition probabilities are also estimated to understand the reason for the observed PL properties, revealing the higher nonradiative transition probability resulting from concentration quenching due to the starting chemical of MnO2. Ab initio calculations are also performed on the electronic structure of the host crystals of the end members of the obtained compounds, K2Ge4O9 and Rb2Ge4O9. The optical bandgap calculated varies between K and Rb, while the observed ones are not sensitive to the K content x. Nevertheless, they are high enough for the optimal red emission of Mn4+ ions via an excitation of 4A2g–4T1g or 4T2g.

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High energy density layered-spinel hybrid cathodes for lithium ion rechargeable batteries

Cited by 9 publications

References 27 publications

Synthesis and Electrochemical Characterization of a Li-Rich Li_1.17Ni_0.34Mn_0.5O₂Cathode Material for Lithium-Ion Cells

Synthesis and Electrochemical Characterization of a Li-Rich Li_1.17Ni_0.34Mn_0.5O₂Cathode Material for Lithium-Ion Cells

Facile Electrochemical Activity of Monoclinic Li₂MnSiO₄as Potential Cathode for Li-Ion Batteries

Novel Findings on the Optical Properties of Mn⁴⁺‐Doped (Rb,K)₂Ge₄O₉ Phosphors

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High energy density layered-spinel hybrid cathodes for lithium ion rechargeable batteries

Cited by 9 publications

References 27 publications

Synthesis and Electrochemical Characterization of a Li-Rich Li1.17Ni0.34Mn0.5O2Cathode Material for Lithium-Ion Cells

Synthesis and Electrochemical Characterization of a Li-Rich Li1.17Ni0.34Mn0.5O2Cathode Material for Lithium-Ion Cells

Facile Electrochemical Activity of Monoclinic Li2MnSiO4as Potential Cathode for Li-Ion Batteries

Novel Findings on the Optical Properties of Mn4+‐Doped (Rb,K)2Ge4O9 Phosphors

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Synthesis and Electrochemical Characterization of a Li-Rich Li_1.17Ni_0.34Mn_0.5O₂Cathode Material for Lithium-Ion Cells

Synthesis and Electrochemical Characterization of a Li-Rich Li_1.17Ni_0.34Mn_0.5O₂Cathode Material for Lithium-Ion Cells

Facile Electrochemical Activity of Monoclinic Li₂MnSiO₄as Potential Cathode for Li-Ion Batteries

Novel Findings on the Optical Properties of Mn⁴⁺‐Doped (Rb,K)₂Ge₄O₉ Phosphors