Charge/discharge characteristics of Jahn–Teller distorted nanostructured orthorhombic and monoclinic Li<sub>2</sub>MnSiO<sub>4</sub>cathode materials

Babbar, Prince; Tiwari, Brajesh; Purohit, Bhagyesh; Ivanishchev, Aleksandr V.; Чуриков, А. В.; Dixit, Ambesh

doi:10.1039/c7ra02840g

Cited by 18 publications

(15 citation statements)

References 43 publications

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“…The EDS data of the materials as obtained from HRSEM is summarised in Table S1. The presence of lithium could not be confirmed because of its low atomic mass, which cannot be detected by the instrument [81]. Other elements such as O, P and Fe for LFP and O, Si and Mn for LMS were detected from these materials.…”

Section: Resultsmentioning

confidence: 92%

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Graphenised Lithium Iron Phosphate and Lithium Manganese Silicate Hybrid Cathodes: Potentials for Application in Lithium‐ion Batteries

et al. 2020

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Sol-gel and hand milling techniques were used to prepare a lithium iron phosphate-lithium manganese silicate (LiFePO 4 À Li 2 MnSiO 4) hybrid cathode materials. The structural studies from x-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM) show that the materials are well crystallized although few impurities were observed in the pristine LiFePO 4 (LFP) and Li 2 MnSiO 4 (LMS) materials. We used graphene to coat the hybrid cathode materials in order to increase its conductivity and enhance the electrochemical performance. The successful reduction of the graphene oxide into graphene nanosheets was confirmed with the results from the Fourier transform infrared (FTIR) and Raman spectroscopy. The morphological analysis indicate that the pristine materials are made of spherical nanoparticles that are slightly agglomerated while the sol-gel-prepared hybrid cathode materials show evenly distributed spherical nanoparticles with minimal agglomeration. The in situ sol-gel technique gave more homogenously mixed material in comparison to the hand milling method and particle sizes of 37 and 23 nm respectively were obtained for the plain, and graphenised sol gel derived hybrid materials. The sol-gel derived hybrid materials are also the most thermally stable giving a total weight loss of 4.5 % and 3.4 % for the plain and graphenised cathodes respectively. While the LFP-LMS hybrid cathode materials performed better electrochemically more than the pristine materials in terms of enhanced current and specific capacities, the graphenised LFP-LMS hybrid cathode materials showed better electrochemical properties compared to those without graphene. This is associated with the presence of graphene nanosheets in these samples. All the results confirmed that the graphenised LiFePO 4 À Li 2 MnSiO 4 hybrid cathode material prepared via in situ sol-gel method performed better than those of the hand milling method.

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Section: Resultsmentioning

confidence: 92%

“…Both pristine materials show slightly agglomerated spherical nanoparticles having uniform sizes. These morphologies could affect the electrochemical behaviour of the materials, as they are most likely to cause slow intercalation/de‐intercalation of Li‐ions during charge/discharge processes [81].…”

Section: Resultsmentioning

confidence: 99%

Graphenised Lithium Iron Phosphate and Lithium Manganese Silicate Hybrid Cathodes: Potentials for Application in Lithium‐ion Batteries

et al. 2020

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“…The observed much lower specific capacities for Li 2 FeSiO 4 cathode material is a subject of intensive exploration, as either smaller capacities (extraction/ insertion of only 50% or lesser lithium atoms) or large capacity fading is observed not only in this system but also in similar systems such as Li 2 Mn-SiO 4 systems. 15,21 Thus, it seems that bulk and localized crystal structures are responsible for such capacity fading. Here, iron forms tetrahedra with oxygen, i.e.…”

Section: Resultsmentioning

confidence: 99%

Capacity Fading in Li2FeSiO4 Cathode Material: Intrinsic or Extrinsic

Babbar

Tiwari

Ivanishchev

et al. 2021

Journal of Elec Materi

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We report the origin of capacity fading in Li 2 FeSiO 4 cathode material, while addressing the challenges associated with the synthesis of phase-pure Li 2 FeSiO 4 positive electrode materials in bulk and nanostructured geometries. The process has been optimized to remove iron oxide (Fe 2 O 3) impurities and for effective carbon coating on a Li 2 FeSiO 4 nanostructured core using a carbon source precursor during the synthesis process. X-ray diffraction measurements confirm the phase purity and nanocrystalline nature of synthesized materials. UV-visible spectroscopic measurements are carried out to understand the electronic/optical characteristics, and their correlation with materials' electrochemical performance is investigated. The impact of iron charge state in an FeO 4 tetrahedra configuration is correlated to the electrochemical performance together with the lithium-ion transporting states. The Jahn-Teller active FeO 4 tetrahedra may show structural distortion in the sub-lattice of Li 2 FeSiO 4 with different charge states and may be the main source of capacity fading in Li 2 FeSiO 4 cathode material from the first cycle onwards.

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“…First of all, Mn 2+ is oxidized to Mn 3+ after the first lithium ion extraction from Li 2 MnSiO 4 . The Jahn‐Teller effect of Mn 3+ and the dissolution of manganese could lead to collapse of Li 2 MnSiO 4 structure, and thus hinder the completely embed of lithium ions. Moreover, the huge irreversible capacity loss may be related with the formation of solid electrolyte interphase (SEI) film which will consume some lithium ions.…”

Section: Resultsmentioning

confidence: 99%

“…At the same time, irreversible changes in the structure of Li 2 MnSiO 4 during cycling can also cause the irreversible attenuation of capacity. In addition, the Jahn‐Teller effect that occurs during the transition from Mn 2+ to Mn 4+ is more serious than other cathode materials. It is because of these inherent defects that lead to poor cycling performance of Li 2 MnSiO 4 material.…”

Section: Introductionmentioning

confidence: 99%

Preparation and Electrochemical Properties of Rice Husks Based Li₂MnSiO₄Cathode Materials

et al. 2018

ChemistrySelect

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Porous Li2MnSiO4/C nanocomposite has been synthesized via a solid‐state reaction using rice husks as raw material, in which cubic‐like Li2MnSiO4 nanoparticles are uniformly distributed in the porous carbon layer, as high stability and capacity lithium‐ion cathode materials. Compared to Li2MnSiO4/C, the as‐prepared porous nanocomposite delivers a high initial discharge/charge specific capacity of 479.6/321.9 mAh g−1 at 0.2 C and a superior cycling stability (276.9/242.2 mAh g−1 at 0.2 C after 50 cycles of charge‐discharge cycle). In addition, the porous Li2MnSiO4/C exhibits an excellent rate performance that it still has a discharge specific capacity of 163.2 mAh g−1 even at 1 C. Its outstanding electrochemical properties are attributed to the unique porous carbon nanostructure, which not only improves the conductivity of the material, but also facilitates the transfer of ions in the material. This facile and low‐cost of porous Li2MnSiO4/C cathode material has great potential in the future development of lithium ion batteries.

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Charge/discharge characteristics of Jahn–Teller distorted nanostructured orthorhombic and monoclinic Li₂MnSiO₄cathode materials

Cited by 18 publications

References 43 publications

Graphenised Lithium Iron Phosphate and Lithium Manganese Silicate Hybrid Cathodes: Potentials for Application in Lithium‐ion Batteries

Graphenised Lithium Iron Phosphate and Lithium Manganese Silicate Hybrid Cathodes: Potentials for Application in Lithium‐ion Batteries

Capacity Fading in Li2FeSiO4 Cathode Material: Intrinsic or Extrinsic

Preparation and Electrochemical Properties of Rice Husks Based Li₂MnSiO₄Cathode Materials

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Charge/discharge characteristics of Jahn–Teller distorted nanostructured orthorhombic and monoclinic Li2MnSiO4cathode materials

Cited by 18 publications

References 43 publications

Graphenised Lithium Iron Phosphate and Lithium Manganese Silicate Hybrid Cathodes: Potentials for Application in Lithium‐ion Batteries

Graphenised Lithium Iron Phosphate and Lithium Manganese Silicate Hybrid Cathodes: Potentials for Application in Lithium‐ion Batteries

Capacity Fading in Li2FeSiO4 Cathode Material: Intrinsic or Extrinsic

Preparation and Electrochemical Properties of Rice Husks Based Li2MnSiO4Cathode Materials

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Charge/discharge characteristics of Jahn–Teller distorted nanostructured orthorhombic and monoclinic Li₂MnSiO₄cathode materials

Preparation and Electrochemical Properties of Rice Husks Based Li₂MnSiO₄Cathode Materials