Multielectron, Cation and Anion Redox in Lithium-Rich Iron Sulfide Cathodes

Hansen, C.; Zak, Joshua J.; Martinolich, Andrew J.; Ko, Jesse S.; Bashian, Nicholas H.; Kaboudvand, Farnaz; Ven, Anton Van der; Melot, Brent C.; Weker, Johanna Nelson; See, Kimberly A.

doi:10.1021/jacs.0c00909

Cited by 69 publications

(224 citation statements)

References 74 publications

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“…23 , 25 , 26 Recent work has also shown that anion redox involving sulfur can be important in controlling reaction pathways. For example, sulfides such as VS 4 27 , 28 and Li 2 FeS 2 29 undergo reversible ion intercalation/deintercalation reactions involving coupled S 2– /S 2 2– beside transition-metal redox couples.…”

Section: Introductionmentioning

confidence: 99%

Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

et al. 2021

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The electrochemical lithiation and delithiation of the layered oxysulfide Sr 2 MnO 2 Cu 4−δ S 3 has been investigated by using a combination of in situ powder X-ray diffraction and ex situ neutron powder diffraction, X-ray absorption and 7 Li NMR spectroscopy, together with a range of electrochemical experiments. Sr 2 MnO 2 Cu 4−δ S 3 consists of [Sr 2 MnO 2 ] perovskite-type cationic layers alternating with highly defective antifluorite-type [Cu 4−δ S 3 ] (δ ≈ 0.5) anionic layers. It undergoes a combined displacement/intercalation (CDI) mechanism on reaction with Li, where the inserted Li replaces Cu, forming Li 4 S 3 slabs and Cu + is reduced and extruded as metallic particles. For the initial 2–3% of the first discharge process, the vacant sites in the sulfide layer are filled by Li; Cu extrusion then accompanies further insertion of Li. Mn 2.5+ is reduced to Mn 2+ during the first half of the discharge. The overall charging process involves the removal of Li and re-insertion of Cu into the sulfide layers with re-oxidation of Mn 2+ to Mn 2.5+ . However, due to the different diffusivities of Li and Cu, the processes operating on charge are quite different from those operating during the first discharge: charging to 2.75 V results in the removal of most of the Li, little reinsertion of Cu, and good capacity retention. A charge to 3.75 V is required to fully reinsert Cu, which results in significant changes to the sulfide sublattice during the following discharge and poor capacity retention. This detailed structure–property investigation will promote the design of new functional electrodes with improved device performance.

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Section: Introductionmentioning

confidence: 99%

Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

et al. 2021

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“…[16] Recently,Saha et al presented fundamental research on the bottlenecks of Sr edox, [17] in which an ew material Li 1.33À2y/3 Ti 0.67Ày/3 Fe y S 2 (y = 0.3) was capable of ar eversible capacity as high as 245 mAh g À1 .T he high capacity resulted from the existence of 3d 6 electrons in the Fe 2+/3+ redox couple that activated the anionic Sr edox. During the final review stage of this manuscript, See et al revealed the electrochemistry of aL i-rich layered iron sulfide Li 2 FeS 2 , [18] whereas Zhao-Karger reported on multivalent cation storage in VS 4 , [19] further emphasizing the rising importance of this class of materials.…”

Section: Introductionmentioning

confidence: 99%

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

et al. 2020

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We report the electrochemistry of a hitherto unexplored Na2MoS4 phase as a conversion electrode material for Na‐ and Li‐ion batteries. The material adopts an amorphous coordination polymer structure with mixed Mo and S valences. XPS and XRD analysis reveal a complex interplay between Mo and S redox chemistry, while excluding the formation of free sulfur, lithium sulfide, or other crystalline phases. Na2MoS4 behaves as a mixed ionic–electronic conductor, with electronic conductivity of 6.1×10−4 S cm−1, that permits carbon‐free application in an electrochemical cell. A reversible capacity of up to 500 mAh g−1 was attained, corresponding to a five‐electron redox exchange, with species ranging from (highest oxidized state) to 5MoS4> (lowest oxidized state). This study emphasizes the excellent charge‐storage performances of Na2MoS4 for Li‐ or Na‐ion batteries, and enriches the emerging library and knowledge of sulfide phases with mixed anionic and cationic redox properties.

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“…23,25,26 Recent work has also show that anion redox involving sulfur can be important in controlling reaction pathways. For example, sulphides such as VS4 27,28 and FeS2 29 undergo reversible ion intercalation-deintercalation reactions involving coupled S 2− /S 2 2− beside transition-metal redox couples.…”

Section: Introductionmentioning

confidence: 99%

Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

Dey

Zeng²,

Adamson³

et al. 2021

Preprint

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The electrochemical lithiation and delithiation of the layered oxysulfide Sr2MnO2Cu4−δS3 has been investigated by using a combination of in situ powder X-ray diffraction and ex situ neutron powder diffraction, X ray absorption and Li NMR spectroscopy, together with a range of electrochemical experiments. Sr2MnO2Cu4−δS3 consists of [Sr2MnO2] perovskite-type cationic layers alternating with highly defective antifluorite-type [Cu4−dS3] (d ~ 0.5) anionic layers. It undergoes a combined displacement/intercalation (CDI) mechanism on reaction with Li, where the inserted Li replaces Cu, forming Li4S3 slabs and Cu+ is reduced and extruded as metallic particles. For the initial 2-3% of the 1st discharge process, the vacant sites in the sulfide layer are filled by Li; Cu extrusion then accompanies further insertion of Li. Mn2.5+ is reduced to Mn2+ during the first half of the discharge. The overall charging process involves the removal of Li and re-insertion of Cu into the sulfide layers with re-oxidation of Mn2+ to Mn2.5+. However, due to the different diffusivities of Li and Cu, the processes operating on charge are quite different from those operating during the first discharge: charging to 2.75 V results in removal of most of the Li, little reinsertion of Cu and good capacity retention. A charge to 3.75 V is required to fully reinsert Cu, which results in significant changes to the sulfide sublattice during the following discharge and poor capacity retention. This detailed structure-property investigation will promote the design of new functional electrodes with improved device performance.

show abstract

Multielectron, Cation and Anion Redox in Lithium-Rich Iron Sulfide Cathodes

Cited by 69 publications

References 74 publications

Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

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