Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes

Fadel, Eric; Faglioni, Francesco; Samsonidze, Ge. G.; Molinari, Nicola; Merinov, Boris V.; Goddard, William A.; Grossman, Jeffrey C.; Mailoa, Jonathan P.; Kozinsky, Boris

doi:10.1038/s41467-019-11317-3

Cited by 54 publications

(53 citation statements)

References 66 publications

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“…DFT calculations were performed using the M06-HF functional with NWCHEM software. The M06-HF functional was selected as it is a suitable option to capture the charge-density differences of anion-solvent complexes in a physically consistent way (38,39). The initial structures of complexes were extracted from classical molecular-dynamics simulation with COMPASS force field by simulated annealing algorithm (40).…”

Section: Methodsmentioning

confidence: 99%

Role of inner solvation sheath within salt–solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries

Ren

Gao

Zou

et al. 2020

Proc. Natl. Acad. Sci. U.S.A.

263

197

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Functional electrolyte is the key to stabilize the highly reductive lithium (Li) metal anode and the high-voltage cathode for long-life, high-energy-density rechargeable Li metal batteries (LMBs). However, fundamental mechanisms on the interactions between reactive electrodes and electrolytes are still not well understood. Recently localized high-concentration electrolytes (LHCEs) are emerging as a promising electrolyte design strategy for LMBs. Here, we use LHCEs as an ideal platform to investigate the fundamental correlation between the reactive characteristics of the inner solvation sheath on electrode surfaces due to their unique solvation structures. The effects of a series of LHCEs with model electrolyte solvents (carbonate, sulfone, phosphate, and ether) on the stability of high-voltage LMBs are systematically studied. The stabilities of electrodes in different LHCEs indicate the intrinsic synergistic effects between the salt and the solvent when they coexist on electrode surfaces. Experimental and theoretical analyses reveal an intriguing general rule that the strong interactions between the salt and the solvent in the inner solvation sheath promote their intermolecular proton/charge transfer reactions, which dictates the properties of the electrode/electrolyte interphases and thus the battery performances.

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Section: Methodsmentioning

confidence: 99%

Role of inner solvation sheath within salt–solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries

Ren

Gao

Zou

et al. 2020

Proc. Natl. Acad. Sci. U.S.A.

263

197

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“…The first step in the lifetime of a CEI layer is its formation during the initial charge and discharge steps of the battery cell. The SOC has been stated on multiple occasions as an highly influential factor for the CEI: [50,77] Depending, on different starting SOC, different self-discharge currents have been observed as the result of electrolyte decomposition utilizing a "high precision electrochemical measurement device". [36] Density function theory (DFT) supported those findings and determined EC as the main component of parasitic reactions at the surface of cobalt atoms, initiated by the coordination of EC's oxygen atom and a cathode's cobalt atom.…”

Section: Formationmentioning

confidence: 99%

Face to Face at the Cathode Electrolyte Interphase: From Interface Features to Interphase Formation and Dynamics

Kuhn

Edström

Winter

et al. 2022

Adv Materials Inter

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Development of high‐performing lithium‐based batteries inevitably calls for a profound understanding and elucidation of the reactivity at the electrode–liquid electrolyte interface and its impact on the overall performance and safety. The formation, composition, properties, and mechanisms of the cathode electrolyte interphase (CEI) formation and function are still to a large extent unknown for most lithium‐based battery materials, whereas the same is well considered for the solid electrolyte interphase on negative electrodes in the literature. In particular, in high voltage regions >4.3 V, the oxidative stability limit of most liquid electrolytes is reached and new mechanisms, involving surface reactivity of the active material beside electrolyte decomposition, contribute to the interfacial reactivity and nature of the CEI. Focusing on lithium‐based cell chemistries, this review aims to highlight the impact of the still less understood electrolyte decomposition chemistry, dictated by the nature of its components, as well as the in‐depth research on the physicochemical and electrochemical properties of CEI formation and evolution at positive electrode material surface and sub‐surfaces.

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“…The retained reversible capacity illustrates the stability of the crystal framework at a high current density. It is noteworthy to mention here that the difference in charge‐discharge capacity is prominent in the case of low current rate (40 mA g −1 ) cycling and make us assume that the phenomenon is due to oxidation of perchlorate anion at higher voltage and gets aggravated with the higher time of exposure [36] …”

Section: Resultsmentioning

confidence: 84%

Zirconium‐Doped Vanadium Oxide and Ammonium Linked Layered Cathode to Construct a Full‐Cell Magnesium‐Ion Battery: A Realization and Structural, Electrochemical Study

Muthuraj

Sarkar

Panda

et al. 2021

Batteries & Supercaps

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More than three times higher bulk density, easy to handle in air, and high abundance on earth crust make magnesium metal a desirable element in battery application. Several efforts have been attempted to construct the rechargeable magnesium‐ion battery, unfortunately none of them are successful to a limit. Here, a new generation of vanadium oxide linked with ammonium ions is considered an active cathode for magnesium ion insertion. The Zr doped‐NH4V4O10 (Zr‐NVO) nanorod exhibits an initial discharge capacity of 328 mAh g−1 at 40 mA g−1 current density with negligible capacity fading till 150 cycles. The estimated Mg2+ diffusivity in such cathode is found to be in the range of 10−11 to 10−12 cm2 s−1, demonstrating a pronounced Mg‐ion mobility in Zr‐NVO cathode. In addition, a detailed mechanistic study is performed at different states of charge using XRD, XPS and in‐situ XANES analysis. In conclusion, to achieve the ultimate goal of such study, a full‐cell is assembled and evaluated by coupling tin anode with magnesiated Zr‐NVO cathode. The cell has been cycled for a limited number of cycles and the reason behind the limited cycling behaviour is discussed and offers us a pathway to a resolution of the problem for rechargeable magnesium‐ion battery development in the near future.

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Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes

Cited by 54 publications

References 66 publications

Role of inner solvation sheath within salt–solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries

Role of inner solvation sheath within salt–solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries

Face to Face at the Cathode Electrolyte Interphase: From Interface Features to Interphase Formation and Dynamics

Zirconium‐Doped Vanadium Oxide and Ammonium Linked Layered Cathode to Construct a Full‐Cell Magnesium‐Ion Battery: A Realization and Structural, Electrochemical Study

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