Thermodynamic stability and correlation with synthesis conditions, structure and phase transformations in orthorhombic and monoclinic Li2M(SO4)2 (M = Mn, Fe, Co, Ni) polymorphs

Radha, A. V.; Lander, Laura; Rousse, Gwenaëlle; Tarascon, J. M.; Navrotsky, Alexandra

doi:10.1039/c4ta05066e

Cited by 25 publications

(24 citation statements)

References 61 publications

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“…The lower redox potential of the tavorite phase compared to the layered one might be ascribed to the fact that 1) the tavorite phase is thermodynamically less stable than its layered counterpart and 2) the oxidized tavorite phase is more stable than the oxidized layered phase due to the increased electrostatic repulsions of the edge‐sharing FeO 6 octahedra in the latter …”

Section: Li‐based Sulfatesmentioning

confidence: 99%

Sulfate‐Based Cathode Materials for Li‐ and Na‐Ion Batteries

Lander

Tarascon

Yamada

2018

The Chemical Record

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Electrochemical energy storage via Li-ion batteries has changed modern life drastically and has enabled technologies such as portable electronic devices, electric vehicles and stationary grid storage. However, with the steadfast technological evolution and increasing energy demands, batteries need to be constantly improved to meet the needs of our society. Furthermore, increasing concerns are raised regarding sustainability, availability of raw materials and cost. Therefore, extensive research efforts have been focused on the development of new battery types leading to the emergence of the Na-ion technology and the discovery of a myriad of new materials. In this context, polyanions became a prominent alternative to layered oxides. A large variety of polyanionic frameworks has been studied in the past years including phosphates, silicates and borates, but it was especially sulfates, which attracted a lot of attention due to their elevated operating voltages. The here presented article gives an overview of the exhaustive research on sulfate-based cathode materials for Li- and Na-ion batteries discussing recent findings and future perspectives.

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Section: Li‐based Sulfatesmentioning

confidence: 99%

Sulfate‐Based Cathode Materials for Li‐ and Na‐Ion Batteries

Lander

Tarascon

Yamada

2018

The Chemical Record

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“…3 ), as reported for similar Li phases. 29 With the exception of Mn 2+ (IR = 0.83 Å), the ionic radii of the divalent metals considered here are fairly similar to each other. We assume that a simple relationship 29 is obscured by the structural variations between the blödite- and kröhnkite-like sulfates.…”

Section: Discussionmentioning

confidence: 56%

“… 29 With the exception of Mn 2+ (IR = 0.83 Å), the ionic radii of the divalent metals considered here are fairly similar to each other. We assume that a simple relationship 29 is obscured by the structural variations between the blödite- and kröhnkite-like sulfates. In addition, the introduction of H 2 O molecules in these structures induces structural depolymerization, as opposed to the anhydrous phases.…”

Section: Discussionmentioning

confidence: 56%

Thermodynamics of the double sulfates Na₂M²⁺(SO₄)₂·nH₂O (M = Mg, Mn, Co, Ni, Cu, Zn,n= 2 or 4) of the blödite–kröhnkite family

2021

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“…This route could only stabilize one of the two possible polymorphs: m -phase (M = Mn) and o -phase (M = Mg, Fe, Co, Zn, and Ni) . For both polymorphs, the positive enthalpy of formation decreased with an increase in the ionic radius of the transition metal center, except for Ni-analogues . Thermal treatment of such compounds resulted in polymorphic transformation barring Mn- and Ni-based phases.…”

Section: Introductionmentioning

confidence: 99%

Marinite Li₂Ni(SO₄)₂ as a New Member of the Bisulfate Family of High-Voltage Lithium Battery Cathodes

et al. 2021

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Development of sustainable, economic, and high-voltage cathode materials forms the cornerstone of cathode design for Li-ion batteries. Sulfate chemistry offers a fertile ground to discover high-voltage cathode materials stemming from a high electronegativity-based inductive effect. Herein, we have discovered a new polymorph of high-voltage m-Li 2 Ni II (SO 4 ) 2 bisulfate using a scalable spray drying route. Neutron and synchrotron diffraction analysis revealed a monoclinic structure (s.g. P2 1 / c, #14) built from corner-shared NiO 6 octahedra and SO 4 tetrahedra locating all Li + in a distinct site. Low-temperature magnetic susceptibility and neutron diffraction measurements confirmed long-range A-type antiferromagnetic ordering in m-Li 2 Ni II (SO 4 ) 2 below 15.2 K following the Goodenough−Kanamori−Anderson rule. In situ X-ray powder diffraction displayed an irreversible (monoclinic → orthorhombic) phase transformation at ∼400 °C. The m-Li 2 Ni II (SO 4 ) 2 framework offers two-dimensional Li + migration pathways as revealed by the bond valence site energy (BVSE) approach. The electronic structure obtained using first-principles (DFT) calculation shows a large electronic band gap (E g ∼ 3.8 eV) with a trapped state near the Fermi energy level triggering polaronic conductivity. As per the DFT study, m-Li 2 Ni II (SO 4 ) 2 can work as a 5.5 V (vs Li + /Li 0 ) cathode for Li-ion batteries, with suitable electrolytes, coupling both cationic (Ni II/III ) and anionic (O − ) redox activity.

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Thermodynamic stability and correlation with synthesis conditions, structure and phase transformations in orthorhombic and monoclinic Li₂M(SO₄)₂ (M = Mn, Fe, Co, Ni) polymorphs

Abstract: Calorimetric studies demonstrate that higher symmetry orthorhombic Li2M(SO4)2 (M = Co, Fe) have lower energetic stability than the corresponding monoclinic phases.

Cited by 25 publications

References 61 publications

Sulfate‐Based Cathode Materials for Li‐ and Na‐Ion Batteries

Sulfate‐Based Cathode Materials for Li‐ and Na‐Ion Batteries

Thermodynamics of the double sulfates Na₂M²⁺(SO₄)₂·nH₂O (M = Mg, Mn, Co, Ni, Cu, Zn,n= 2 or 4) of the blödite–kröhnkite family

Marinite Li₂Ni(SO₄)₂ as a New Member of the Bisulfate Family of High-Voltage Lithium Battery Cathodes

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Thermodynamic stability and correlation with synthesis conditions, structure and phase transformations in orthorhombic and monoclinic Li2M(SO4)2 (M = Mn, Fe, Co, Ni) polymorphs

Abstract: Calorimetric studies demonstrate that higher symmetry orthorhombic Li2M(SO4)2 (M = Co, Fe) have lower energetic stability than the corresponding monoclinic phases.

Cited by 25 publications

References 61 publications

Sulfate‐Based Cathode Materials for Li‐ and Na‐Ion Batteries

Sulfate‐Based Cathode Materials for Li‐ and Na‐Ion Batteries

Thermodynamics of the double sulfates Na2M2+(SO4)2·nH2O (M = Mg, Mn, Co, Ni, Cu, Zn,n= 2 or 4) of the blödite–kröhnkite family

Marinite Li2Ni(SO4)2 as a New Member of the Bisulfate Family of High-Voltage Lithium Battery Cathodes

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Thermodynamic stability and correlation with synthesis conditions, structure and phase transformations in orthorhombic and monoclinic Li₂M(SO₄)₂ (M = Mn, Fe, Co, Ni) polymorphs

Thermodynamics of the double sulfates Na₂M²⁺(SO₄)₂·nH₂O (M = Mg, Mn, Co, Ni, Cu, Zn,n= 2 or 4) of the blödite–kröhnkite family

Marinite Li₂Ni(SO₄)₂ as a New Member of the Bisulfate Family of High-Voltage Lithium Battery Cathodes