Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries

Strmčnik, Dušan; Castelli, Ivano E.; Connell, Justin G.; Haering, Dominik; Zorko, Milena; Martins, Pedro Farinazzo Bergamo Dias; Lopes, Pietro Papa; Genorio, Boštjan; Østergaard, Thomas M.; Gasteiger, Hubert A.; Maglia, Filippo; Antonopoulos, Byron K.; Stamenković, Vojislav R.; Marković, Nenad M.

doi:10.1038/s41929-018-0047-z

Cited by 161 publications

(246 citation statements)

References 51 publications

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“…Apart from residual LiPF 6 , we tentatively attribute these fluorine concentrations to thin, non‐passivating LiF films formed via HF reduction. We recently demonstrated, that such films form at potentials >1 V, and that their formation requires electrocatalytically active sites, of which HOPG has few .Hence our formation potential should have little influence on them, so that no trend was to be expected in the first place.…”

Section: Resultsmentioning

confidence: 91%

Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite

Antonopoulos

Maglia

Schmidt-Stein

et al. 2018

Batteries & Supercaps

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The solid electrolyte interphase (SEI) on graphite anodes is a key enabler for rechargeable lithium-ion batteries (LIBs). It ensures that only Li + ions and no damaging electrolyte components enter the anode and hinders electrolyte decomposition. Its growth should be confined to the initial SEI formation process and stop once the battery is in operation to avoid capacity/ power loss. In technical LIB cells, the SEI is formed at constant current, with the potential of the graphite anode slowly drifting from higher to lower voltages. SEI formation rate, composition, and structure depend on the potential and on the chemical properties of the anode surface. Here, we characterize SEIs formed at constant potentials on the chemically inactive basal plane of highly oriented pyrolytic graphite (HOPG). X-ray photoemission spectroscopy (XPS) detects carbonate species only at lower formation potentials. Cyclic voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) with Fc/Fc + as an electrochemical probe demonstrate how the formation potential influences ion transport and electrochemical kinetics to and at the anode surface, respectively. Breaking the EIS data down to a Distribution of Relaxation Times (DRT) reveals distinct kinetics and transport related peaks with varying Arrhenius-type temperature dependencies. We discuss our findings in the context of previous electrochemical studies and existing SEI models and of SEI formation protocols suitable for industry.

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Section: Resultsmentioning

confidence: 91%

Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite

Antonopoulos

Maglia

Schmidt-Stein

et al. 2018

Batteries & Supercaps

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“…In our article, we focus on the structural aspects of the SEI, in particular, on the compact layer of the SEI which may cause rate limitations in Li-ion batteries. 29 We anticipate that determining the structure and resulting materials properties may provide the information useful for optimizing the SEI. This is the first study reporting a detailed atomistic description of the SEI structure formed at the interface of Li with an IL.…”

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confidence: 99%

Interface Structure in Li-Metal/[Pyr₁₄][TFSI]-Ionic Liquid System from ab Initio Molecular Dynamics Simulations

Merinov

Zybin

Naserifar

et al. 2019

J. Phys. Chem. Lett.

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Ionic liquids (ILs) are promising materials for application in a new generation of Li-batteries. They can be used as electrolyte, interlayer, or incorporated into other materials. ILs have ability to form a stable Solid Electrochemical Interface (SEI) which plays an important role, preventing Li-based electrode from oxidation and electrolyte from extensive decomposition. Experimentally, it is hardly possible to elicit fine details of the SEI structure. To remedy this situation, we have performed a comprehensive computational study (DFT-MD) to determine the composition and structure of the SEI compact layer formed between Li anode and [Pyr14][TFSI] IL. We found that the [TFSI] anions quickly reacted with Li and decomposed, unlike the [Pyr14] cations which remained stable. The obtained SEI compact layer structure is non-homogeneous and consists of the atomized S, N, O, F, and C anions oxidized by Li atoms.

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“…[73,74] Another typical decomposition product of NaOTf, CF x , mainly exists in the outer surface of the SEI in PGM-T, and this also hinders sodium ion diffusion. [75][76][77][78] All these results demonstrate that the Al 2 O 3 deactivating of defects protects them and forms a more effective SEI, contributing to better electrochemical performance. This together with SEI analyses results in the conclusion that the SEI formed on Al 2 O 3 /PGM-5 has a higher sodium ion conductivity than that on PGM-T.…”

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confidence: 99%

Deactivating Defects in Graphenes with Al₂O₃ Nanoclusters to Produce Long‐Life and High‐Rate Sodium‐Ion Batteries

Lin

Zhang

Kong

et al. 2018

Advanced Energy Materials

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LIBs), delivers very limited reversible capacity in SIBs due to its inability to form stable low-stage graphite intercalation compounds (GICs). [4,5] Thus, most research has turned to nongraphitic carbons including nanocarbons and hard carbons, [6][7][8][9][10] whose capacities are significantly higher than graphite. It has been found that the structure could be well controlled to realize the high efficiency and reversibility. Our group has reported that the commercial carbon molecular sieves with abundant ultrasmall (0.3-0.5 nm) pores can achieve high efficiency and reversible capacity. [11] Intensive researches have also revealed that the nongraphitic carbons with low specific surface areas (SSA) exhibit a high electrochemical stability. [12][13][14][15][16] However, these carbons show limited rate capability and relatively low capacity. Thus, it is desired to improve the SSA to enhance the rate performance and capacity. Unfortunately, nongraphitic carbons with large SSA and a large number of defects typically exhibit an extremely low initial Coulombic efficiency (ICE) and unsatisfactory cyclic stability because of uncontrollable electrolyte decomposition and ineffective formation of a solid electrolyte interphase (SEI). In a previous report, we used reduced graphene oxide (rGO) as a model anode and found that an ether-based electrolyte can greatly suppress the Carbon materials are the most promising anodes for sodium-ion batteries (SIBs), but low initial Coulombic efficiency (ICE) and poor cyclic stability hinder their practical use. It is shown herein, that an effective but simple remedy for these problems can be achieved by deactivating defects in the carbon with Al 2 O 3 nanocluster coverage. A 3D porous graphene monolith (PGM) is used as the model material and Al 2 O 3 nanoclusters around 1 nm are grown on the defects of graphene. It is shown that these Al 2 O 3 nanoclusters suppress the decomposition of conductive sodium salt in the electrolyte, resulting in the formation of a thin and homogenous solid electrolyte interphase (SEI). In addition, Al 2 O 3 nanoclusters appear to reduce the detrimental etching of the SEI by hydrogen fluoride (HF) and improve its stability. Therefore, after the introduction of Al 2 O 3 nanoclusters, the ICE, cyclic stability, and rate capability of the PGM are greatly improved. A higher ICE (70.2%) and capacity retention (82.9% after 500 cycles at 0.5 A g −1 ) than those of normally reported for large surface area carbons are achieved. This work indicates a new way to deactivate defects and modify the SEI of carbon materials, and hopefully accelerate the commercialization of carbon materials as anode materials for SIBs.

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Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries

Cited by 161 publications

References 51 publications

Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite

Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite

Interface Structure in Li-Metal/[Pyr₁₄][TFSI]-Ionic Liquid System from ab Initio Molecular Dynamics Simulations

Deactivating Defects in Graphenes with Al₂O₃ Nanoclusters to Produce Long‐Life and High‐Rate Sodium‐Ion Batteries

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Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries

Cited by 161 publications

References 51 publications

Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite

Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite

Interface Structure in Li-Metal/[Pyr14][TFSI]-Ionic Liquid System from ab Initio Molecular Dynamics Simulations

Deactivating Defects in Graphenes with Al2O3 Nanoclusters to Produce Long‐Life and High‐Rate Sodium‐Ion Batteries

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Product

Resources

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Interface Structure in Li-Metal/[Pyr₁₄][TFSI]-Ionic Liquid System from ab Initio Molecular Dynamics Simulations

Deactivating Defects in Graphenes with Al₂O₃ Nanoclusters to Produce Long‐Life and High‐Rate Sodium‐Ion Batteries