Solid electrolyte interphase formation on metallic lithium

Lewandowski, Andrzej; Swiderska‐Mocek, Agnieszka; Waliszewski, Lukasz

doi:10.1007/s10008-012-1786-4

Cited by 10 publications

(8 citation statements)

References 42 publications

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“…A low frequency tail on the Nyquist plot is usually seen when lithium is in contact with alkylcarbonate solvents 11,13 or even polymer membranes (Li-PEO-LiTFSI/Li system).…”

Section: Resultsmentioning

confidence: 99%

Reactivity of Succinic Anhydride at Lithium and Graphite Electrodes

Charton

Santos-Peña

Biller

et al. 2017

J. Electrochem. Soc.

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Succinic anhydride (SA) is an useful electrolyte additive for high voltage cathodes but has also a negative impact on graphite (Gr) or Li anodes. For this reason, the Li/electrolyte and Gr/electrolyte interfaces were investigated at 20 • C and 45 • C using half or symmetrical cells. When SA is added at 1% by weight to the electrolyte (alkylcarbonate mixture + LiPF 6 ), an increase in the Li/Li cell impedance at 20 • C occurs owing to the formation of a resistive solid electrolyte interphase (SEI), composed of an inorganic inner layer and an organic outer layer, whereas at 45 • C or in absence of SA, the interphase is more inorganic in nature. The reversible capacity of graphite, cycled in Gr/Li half-cells in the presence of SA, is very low at 20 • C but almost ten times larger at 45 • C. Cycling symmetrical Gr/Gr cells at 45 • C indicates that Gr capacity is lower in the presence of SA in connection with the presence of an organic and polymer rich SEI. GC-MS analysis of the electrolyte after cycling shows that ethylene glycol bis-(alkylcarbonate) derivatives disappear when SA is present, owing to the ability of SA to react with lithium alkoxides to yield oligopolyester. Lithium ion batteries (LIBs) are a reliable way to store electric energy, with high gravimetric and volumetric energy density, which allows their application in nomad systems including electric and/or hybrid vehicles. However, electric vehicles range is unsuitable for most of the consumers and, therefore, energy density should be improved. In the past twenty years, many researches have been performed on electrode materials and electrolytes with the aim to enhance battery performance. Use of 5V class positive electrodes (cathodes) is a convenient way to increase LIBs energy density. It explains the development of promising "high voltage" materials like Li 3 V 2 (PO 4 ) 3 , 1 Li 2 CoPO 4 F 2 or the LiNi 0.5 Mn 1.5 O 4 (LNMO) 3 spinel. Nevertheless, the use of new cathodes operating at high voltage leads to the degradation of the battery electrolyte, usually based on a mixture of cyclic and linear alkylcarbonates containing LiPF 6 as salt and functional additives. Unfortunately, standard electrolytes are oxidized on 5 V cathodes and this significantly limits the battery cycling life. From the first cycles, electrolyte components degrade forming by-products, which in turn, can interact with electrodes surface. As an example, a passive layer is formed on graphite (Gr)/electrolyte interface at the first charge. This layer, known as the Solid Electrolyte Interphase (SEI), has a strong impact on the LIBs performances. Electrolyte formulation influences the chemical nature and structure of the SEI. With the aim to improve SEI quality and stability, SEI-forming additives like vinylene carbonate (VC) are generally added to the electrolyte in low amount (less than 5% by weight). These additives are designed to generate a protective passive layer on the active material surface preventing continuous electrolyte decomposition reactions.Whereas additives can be ...

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“…A low frequency tail on the Nyquist plot is usually seen when lithium is in contact with alkylcarbonate solvents 11,13 or even polymer membranes (Li-PEO-LiTFSI/Li system).…”

Section: Resultsmentioning

confidence: 99%

Reactivity of Succinic Anhydride at Lithium and Graphite Electrodes

Charton

Santos-Peña

Biller

et al. 2017

J. Electrochem. Soc.

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“…These reactive monomers form an electrochemically stable and organic rich polymer layer, upon electrochemical reduction at ~0.9 V vs Li/Li + . This group of additives contains, amongst others, vinylene carbonate (VC) [42,43], fluoroethylene carbonate (FEC) [44], vinylene ethylene carbonate [45,46], methyl cinnamate [47], vinyl-containing silane-based compounds [48], and furan derivates [49]. The polymerization of vinylene carbonate (VC) occurs at the carbon-carbon double bond (C--C).…”

Section: In-situ Sei With Additives/electrolytementioning

confidence: 99%

Current status and future perspectives of lithium metal batteries

Varzi

Thanner

Scipioni

et al. 2020

Journal of Power Sources

132

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“…The initial impedance of samples with base-, HDI-, NMP-, NMP–HDI-added electrolytes are all lower than 100 Ω (Figure S7). In the work reported, HDI presents good wettability in LIBs, which may be helpful for the precycling impedance, and the NMP electrolyte generates spherical particles on the Li metal naturally, which is different from the SEI formed electrochemically and shows smaller precycling impedance . After cycling at 0.1 mA cm –2 , the interfacial impedance of cells with base-, HDI-, NMP-added electrolytes are all increased, and the impedance of NMP–HDI-added samples presents a sharp decline as compared to the beginning (Figure S8).…”

Section: Resultsmentioning

confidence: 88%

Amide-Based Interface Layer with High Toughness In Situ Building on the Li Metal Anode

Wang

Sun

Zhou

et al. 2020

ACS Appl. Mater. Interfaces

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Lithium metal is considered to be the ultimate anode for lithium-ion batteries (LIBs) because of its ultrahigh capacity and lowest electrochemical potential. However, the high reactivity of the lithium metal triggers continuous electrolyte consumption and dendrite growth, resulting in short cycle lifetime and serious safety issues. Massive efforts have been made to stabilize the surface of the lithium metal anode. Here, we propose an amide-based passivation layer to serve as an electrochemically stable and highly tough SEI on the lithium metal anode by in situ generation. The SEI layer presents a high elasticity modulus of 10 GPa and enables stable cycling in 2500 h. Furthermore, based on our strategy, the Li/LiFePO 4 cell with a cathode loading of ∼19 mg cm −2 exhibits a long lifespan of 400 cycles. Our approach establishes a meaningful guideline for building a highly strong electrolyte/electrode interface in high-energy density lithium metal batteries.

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Solid electrolyte interphase formation on metallic lithium

Cited by 10 publications

References 42 publications

Reactivity of Succinic Anhydride at Lithium and Graphite Electrodes

Reactivity of Succinic Anhydride at Lithium and Graphite Electrodes

Current status and future perspectives of lithium metal batteries

Amide-Based Interface Layer with High Toughness In Situ Building on the Li Metal Anode

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