Molecular-Level Insights into the Reactivity of Siloxane-Based Electrolytes at a Lithium-Metal Anode (original) (raw)
Related papers
ACS Applied Energy Materials, 2019
One of the major bottlenecks to the development of alternatives to existing Li ion battery technology, such as Li metal or multivalent ion (Mg, Ca, Zn, or Al) batteries, has to do with the layer of inorganic and organic compounds that forms at the interface between the metallic anode and electrolyte via solvent and salt decomposition (the solid− electrolyte interphase or SEI). In Li metal batteries the growth of dendrites causes continual formation of new SEI, while in multivalent ion batteries the SEI does not allow for the diffusion of the ions. Finding appropriate electrolytes for such systems and gaining an understanding of SEI formation is therefore critical to the development of secondary Li metal and multivalent ion cells. In this work, we use ab initio molecular dynamics simulations to investigate the initial stages of decomposition of organic electrolytes based on ethylene carbonate (EC) and formation of the SEI on Li, Ca, and Al metal surfaces. We first find that pure EC only decomposes to CO and C 2 H 4 O 2 2− species on each type of surface. However, when a salt molecule is introduced to form an electrolyte, a second EC decomposition route resulting in the formation of CO 3 2− and C 2 H 4 begins to occur; furthermore, a variety of different inorganic compounds, depending on the chemical composition of the salt, form on the surfaces. Finally, we find that EC breaks down more quickly on Li and Ca surfaces than on Al and show that this is because the rate of charge transfer is much faster owing to their lower electronegativity and ionization energies. The molecular level understanding of decomposition and SEI formation generated by this computational modeling can lead to the design of new electrolytes for beyond-Li ion batteries.
The Journal of Physical Chemistry C, 2012
Li−O 2 cells composed of a carbon cathode containing an α-MnO 2 nanowire catalyst and a Kynar (PVDF-HFP) binder were cycled with different electrolytes containing 0.5 M LiB(CN) 4 salt in polyethylene glycol dimethyl ether (PEGDME) or tetraethylene glycol dimethyl ether (Tetraglyme) solvents. All cells exhibited fast capacity fading. To explain this, the surface chemistry of the carbon electrodes were investigated by synchrotron based hard X-ray photoelectron spectroscopy (HAXPES) using two photon energies of 2300 and 6900 eV. It is shown that the LiB(CN) 4 salt and Kynar binder were degraded during cycling, forming a layer composed of salt and binder residues on the cathode surface. The degradation mechanism of the salt differed in the two tested solvents and, consequently, different types of boron compounds were formed during cycling. Larger amounts of the degraded salt was observed using Tetraglyme as the solvent. With a nonfluorined Li-salt, the observed formation of LiF, which might be a reason for the observed blockage of pores in the cathode and for the observed capacity fading, must be due to Kynar binder decomposition. The amount of LiF formed in the PEGDME cell was larger than that formed in the Tetraglyme cell. The results indicate that not only the electrolyte solvent, but also electrolyte salt as well as the binder used for the porous cathode must be carefully considered when building a successful rechargeable Li−O 2 battery.
Interfaces and Materials in Lithium Ion Batteries: Challenges for Theoretical Electrochemistry
Topics in current chemistry (Cham), 2018
Energy storage is considered a key technology for successful realization of renewable energies and electrification of the powertrain. This review discusses the lithium ion battery as the leading electrochemical storage technology, focusing on its main components, namely electrode(s) as active and electrolyte as inactive materials. State-of-the-art (SOTA) cathode and anode materials are reviewed, emphasizing viable approaches towards advancement of the overall performance and reliability of lithium ion batteries; however, existing challenges are not neglected. Liquid aprotic electrolytes for lithium ion batteries comprise a lithium ion conducting salt, a mixture of solvents and various additives. Due to its complexity and its role in a given cell chemistry, electrolyte, besides the cathode materials, is identified as most susceptible, as well as the most promising, component for further improvement of lithium ion batteries. The working principle of the most important commercial elect...
Radical Decomposition of Ether-Based Electrolytes for Li-S Batteries
Journal of The Electrochemical Society, 2017
In this work, the stability of ether-based electrolytes for Li-S batteries is investigated with particular regard to the effect of dissolved oxygen. Specifically, the performance of two different electrolyte solvents, i.e., 1,2-dimethoxyethane and its mixture with 1,3-dioxolane (DME:DOL, 1:1 v/v), is characterized in cells assembled in dry air environment, which would substantially lower production costs with respect to inert atmosphere (Ar). Although stability of all the components would suggest that Li-S batteries built in both the environments should behave similarly, it is found that cells containing the DME:DOL-based electrolyte are rather unstable in the presence of O 2 in contrast to those employing DME-based electrolyte, which show a relatively good performance. The different sensitivity toward O 2 of these electrolytes is associated to the ring-opening reaction of DOL, which happens to a greater extent when O 2 is present, but occurs also in its absence. Based on these results a mechanism for electrolyte degradation in Li-S cells, and its reaction with dissolved polysulfides is proposed, which rationally explain for the first time the behavior already reported in literature for these kind of batteries. These findings are also relevant to the field of Li-O 2 batteries, where these ether-based electrolytes are also used.
A Study of the Influence of Lithium Salt Anions on Oxygen Reduction Reactions in Li-Air Batteries
Journal of the Electrochemical Society
The influence of lithium salts on O 2 reduction reactions (ORR) in 1, 2-dimethoxyethane (DME) and tetraethylene glycol dimethyl ether (TEGDME) has been investigated. Microelectrode studies in a series of tetrabutylammonium salt (TBA salt)/DME-based electrolytes showed that O 2 solubility and diffusion coefficient are not significantly affected by the electrolyte anion. The ORR voltammograms on microelectrodes in these electrolytes exhibited steady-state limiting current behavior. In contrast, peak-shaped voltammograms were observed in Li +-conducting electrolytes suggesting a reduction of the effective electrode area by passivating ORR products as well as migration-diffusion control of the reactants at the microelectrode. FT-IR spectra have revealed that Li + ions are solvated to form solvent separated ion pairs of the type Li + (DME) n PF 6 − and Li + (TEGDME)PF 6 − in LiPF 6-based electrolytes. On the other hand, the contact ion pairs (DME) m Li + (CF 3 SO 3 −) and(TEGDME)Li + (CF 3 SO 3 −) appear to form in LiSO 3 CF 3containing electrolytes. In the LiSO 3 CF 3-based electrolytes the initial ORR product, superoxide (O 2 −), is stabilized in solution by forming [(DME) m-1 (O 2 −)]Li + (CF 3 SO 3 −) and [(TEGDME)(O 2 −)]Li + (CF 3 SO 3 −) complexes. These soluble superoxide complexes are able to diffuse away from the electrode surface reaction sites to the bulk electrolyte in the electrode pores where they decompose to form Li 2 O 2. This explains the higher capacity obtained in Li/O 2 cells utilizing LiCF 3 SO 3 /TEGDME electrolytes.
LithiumOxygen Electrochemistry in Non-Aqueous Solutions
Israel Journal of Chemistry, 2015
Pairing lithium and oxygen in aprotic solvents can theoretically lead to one of the most promising electrochemical cells available. If successful, this system could compete with technologies such as the internal combustion engine and provide an energy density that can accommodate electric vehicle demands. However, there are many problems that have inhibited this technology from becoming realistic. One of the main reasons is capacity fading after only a few cycles, which is caused by the instability of electrolyte solutions in the presence of reduced oxygen species like O 2 C À and O 2 2À. In recent years, using various analytical tools, researchers have been able to isolate the breakdown products arising from the reactions occurring between the aprotic solvent and the reduced oxygen species. Nevertheless, no solvents have yet been found that are fully stable throughout the reduction and oxidation processes. However, an understanding of these decomposition mechanisms can help us in designing new systems that are more stable toward the aggressive conditions taking place in LiÀO 2 cell operation. This review will include analytical studies on the most widely used solvents in current LiÀO 2 research.
The Journal of Physical Chemistry Letters, 2013
Polyether solvents are considered interesting and important candidates for Li−O 2 battery systems. Discharge of Li−O 2 battery systems forms Li oxides. Their mechanism of formation is complex. The stability of most relevant polar aprotic solvents toward these Li oxides is questionable. Specially high surface area carbon electrodes were developed for the present work. In this study, several spectroscopic tools and in situ measurements using electrochemical quartz crystal microbalance (EQCM) were employed to explore the discharge−charge processes and related side reactions in Li−O 2 battery systems containing electrolyte solutions based on triglyme/lithium bis-(trifluoromethanesulfonyl)imide (LiTFSI) electrolyte solutions. The systematic mechanism of lithium oxides formation was monitored. A combination of Fourier transform infrared (FTIR), NMR, and matrix-assisted laser desorption/ionization (MALDI) measurements in conjunction with electrochemical studies demonstrated the intrinsic instability and incompatibility of polyether solvents for Li−air batteries. SECTION: Energy Conversion and Storage; Energy and Charge Transport
The Journal of Physical Chemistry B, 2005
The density functional theory (DFT) calculations have been performed for the reduction decompositions of solvents widely used in Li-ion secondary battery electrolytes, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonates (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC), including a typical electrolyte additive, vinylene carbonate (VC), at the level of B3LYP/6-311+G(2d,p), both in the gas phase and solution using the polarizable conductor calculation model. In the gas phase, the first electron reduction for the cyclic carbonates and for the linear carbonates is found to be exothermic and endothermic, respectively, while the second electron reduction is endothermic for all the compounds examined. On the contrary, in solution both first and second electron reductions are exothermic for all the compounds. Among the solvents and the additive examined, the likelihood of undergoing the first electron reduction in solution was found in the order of EC > PC > VC > DMC > EMC > DEC with EC being the most likely reduced. VC, on the other hand, is most likely to undergo the second electron reduction among the compounds, in the order of VC > EC > PC. Based on the results, the experimentally demonstrated effectiveness of VC as an excellent electrolyte additive was discussed. The bulk thermodynamic properties of two dilithium alkylene glycol dicarbonates, dilithium ethylene glycol dicarbonate (Li-EDC) and dilithium 1,2-propylene glycol dicarbonate (Li-PDC), as the major component of solid-electrolyte interface (SEI) films were also examined through molecular dynamics (MD) simulations in order to understand the stability of the SEI film. It was found that film produced from a decomposition of EC, modeled by Li-EDC, has a higher density, more cohesive energy, and less solubility to the solvent than the film produced from decomposition of PC, Li-PDC. Further, MD simulations of the interface between the decomposition compound and graphite suggested that Li-EDC has more favorable interactions with the graphite surface than Li-PDC. The difference in the SEI film stability and the behavior of Li-ion battery cycling among the solvents were discussed in terms of the molecular structures.
Effects of Electrolyte Salts on the Performance of Li–O 2 Batteries
The Journal of Physical Chemistry C, 2013
The effects of lithium salts on the performance of Li−O 2 batteries and the stability of salt anions in the O 2 atmosphere during discharge/charge processes were systematically investigated by studying seven common lithium salts in tetraglyme as electrolytes for Li−O 2 batteries. The discharge products of Li−O 2 reactions were analyzed by X-ray diffraction, Xray photoelectron spectroscopy, and nuclear magnetic resonance spectroscopy. The performance of Li−O 2 batteries was strongly affected by the salt used in the electrolyte. Lithium tetrafluoroborate (LiBF 4 ) and lithium bis(oxalato)borate (LiBOB) decomposed and formed LiF and lithium oxalate, respectively, as well as lithium borates during discharge of Li−O 2 batteries. In the case of other salts, including lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiTf), lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), and lithium bromide (LiBr), the discharge products mainly consisted of Li 2 O 2 and carbonates with minor signs of decomposition of LiTFSI, LiTf, and LiPF 6 . LiBr and LiClO 4 showed the best stability during the discharge process. For the cycling performance, LiTf and LiTFSI were the best among the studied salts. In addition to the instability of lithium salts, decomposition of tetraglyme solvent was a more significant factor contributing to the limited cycling stability. Thus, a more stable nonaqueous electrolyte including organic solvent and lithium salt still needs to be further developed to reach a fully reversible Li−O 2 battery.
Reaction chemistry in rechargeable Li-O2 batteries
Chemical Society reviews, 2017
The seemingly simple reaction of Li-O2 batteries involving lithium and oxygen makes this chemistry attractive for high-energy-density storage systems; however, achieving this reaction in practical rechargeable Li-O2 batteries has proven difficult. The reaction paths leading to the final Li2O2 discharge products can be greatly affected by the operating conditions or environment, which often results in major side reactions. Recent research findings have begun to reveal how the reaction paths may be affected by the surrounding conditions and to uncover the factors contributing to the difficulty in achieving the reactions of lithium and oxygen. This progress report describes the current state of understanding of the electrode reaction mechanisms in Li-O2 batteries; the factors that affect reaction pathways; and the effect of cell components such as solvents, salts, additives, and catalysts on the discharge product and its decomposition during charging. This comprehensive review of the r...