The cathode–electrolyte interface in the Li-ion battery

Edström, Kristina; Gustafsson, Torbjörn; Thomas, John O.

doi:10.1016/j.electacta.2004.03.049

Cited by 822 publications

(741 citation statements)

References 33 publications

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“…A minor component with binding energy of ∼ 685 eV, which corresponds to LiF, was also observed. The formation of LiF was reported by Edström et al, 25 on fresh laminates (with no previous contact with the electrolyte), which was attributed to dehydrofluorination reaction in the binder PVDF, generating HF, which then reacts with Li from the active material or surface Li 2 CO 3 to form LiF. Another small component with binding energy at ∼ 689 eV, which we attributed to the formation of CF 2 -CF 2 was observed only in the data collected with Mg X-rays.…”

Section: O 1s Region-as Shown Inmentioning

confidence: 89%

Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Mansour

Kwabi

Quinlan

et al. 2016

J. Electrochem. Soc.

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X-ray photoelectron spectroscopy (XPS) was used to investigate the surface chemistry of high voltage spinel, LiNi 0.5 Mn 1.5 O 4 (LNMO) positive electrodes cycled 5 and 10 times in Li-cells with 1 M LiPF 6 in (3:7) EC:DMC. The XPS spectra were collected using conventional Mg X-rays with energy of 1253.6 eV as well as synchrotron X-rays with energies of 2493.6 and 3498.4 eV in order to examine the depth distribution of various surface chemical species induced during cycling. The XPS spectra revealed a 5 -10 nm surface layer of organic and Li x PF y O z -type species formed as result of electrolyte decomposition, and a comparatively thinner layer composed of transition metal fluorides and LiF. These results suggest that electrolyte decomposition is a major contributor to parasitic reactions in LNMO battery electrochemistry. Limiting electrolyte decomposition with the use of solvents with wide electrochemical stability windows thus comprises a promising strategy for ensuring the practical feasibility of high voltage spinel materials in future Li-ion systems. Rechargeable lithium-ion batteries (LIBs) are among the widest used energy sources for portable electronic devices, but are currently being considered for more energy-dense applications such as electric vehicles and short-term grid support. In order to realize these possibilities, gravimetric energy densities of typical LIBs, which currently provide 400-550 Wh/kg need to be improved. LiNi 0.5 Mn 1.5 O 4 (LNMO) is a particularly promising positive electrode material in this regard, as it operates at an exceptionally high voltage of 4.8 V vs Li + /Li, 1 resulting in an energy density of ∼706 Wh/kg based on a theoretical capacity of 147 mAh/g for 1e − transfer. 2 Such a high voltage is however above the potential at which most LIB electrodes, cell components and electrolytes decompose (>4.2 V vs Li + /Li), and results in the formation of highly resistive parasitic species that hamper battery reversibility and cycle life.In order to design LIBs that are chemically stable enough for practical application, a strong fundamental understanding of electrolyte decomposition and side product formation mechanisms is required. In positive LIB electrodes, battery cycling typically results in an electrode-electrolyte interface (EEI), the study of which can yield mechanistic insights into particularly critical parasitic reaction pathways responsible for poor electrochemical performance.3 Thus, understanding the structure and composition of the surface EEI in LNMObased positive electrodes is key to their commercial realization.Previous studies exploring LNMO performance degradation during cycling have explored the influence of stoichiometry, 4 cation ordering, 4,5 doping 6 and particle morphology. 5,7,8 There have been relatively fewer studies exploring EEI formation in detail, likely owing to the difficulty of characterizing thin layers (typically < 20 nm) of product. Using Raman and Electrochemical Impedance Spectroscopy (EIS) measurements, Aurbach et al. 9 suggested that LNMO...

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Section: O 1s Region-as Shown Inmentioning

confidence: 89%

Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Mansour

Kwabi

Quinlan

et al. 2016

J. Electrochem. Soc.

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“…LiF is the main product. Such phenomena results in capacity fading of these electrodes in solutions, especially at elevated temperatures [42,43].…”

Section: The Inhibition Effect On Transition Metal Dissolutionmentioning

confidence: 99%

Methods for promoting electrochemical properties of LiNil/3Col/3Mnl/3O2 for lithium-ion batteries

Che

Hu²,

et al. 2013

Chin. Sci. Bull.

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“…The salt used in the electrolyte strongly affects the surface film composition and properties. 22,23,32,49,51,52 For example, LiPF 6 yields fluorine compounds that slow down Li + transport into the cathode.…”

Section: -18mentioning

confidence: 99%

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li_xMn₂O₄(100) Surfaces

2012

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Density functional theory and ab initio molecular dynamics simulations are applied to investigate the initial steps of ethylene carbonate (EC) decomposition on spinel Li 0.6 Mn 2 O 4 (100) surfaces. EC is a key component of the electrolyte used in lithium ion batteries. We predict an slightly exothermic EC bond breaking event on this oxide facet, which facilitates subsequent EC oxidation and proton transfer to the oxide surface. Both the proton and the partially decomposed EC fragment weaken the Mn-O ionic bonding network. Implications for interfacial film made of decomposed electrolyte on cathode surfaces, and Li x Mn 2 O 4 dissolution during power cycling, are discussed. keywords: lithium ion batteries; lithium manganate; ethylene carbonate; density functional theory; ab initio molecule dynamics; computational electrochemistry 1

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The cathode–electrolyte interface in the Li-ion battery

Cited by 822 publications

References 33 publications

Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Methods for promoting electrochemical properties of LiNil/3Col/3Mnl/3O2 for lithium-ion batteries

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li_xMn₂O₄(100) Surfaces

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The cathode–electrolyte interface in the Li-ion battery

Cited by 822 publications

References 33 publications

Probing the Electrode-Electrolyte Interface in Cycled LiNi0.5Mn1.5O4by XPS Using Mg and Synchrotron X-rays

Probing the Electrode-Electrolyte Interface in Cycled LiNi0.5Mn1.5O4by XPS Using Mg and Synchrotron X-rays

Methods for promoting electrochemical properties of LiNil/3Col/3Mnl/3O2 for lithium-ion batteries

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on LixMn2O4(100) Surfaces

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Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li_xMn₂O₄(100) Surfaces