Pathway of in situ polymerization of 1,3-dioxolane in LiPF6 electrolyte on Li metal anode

Xie, Miao; Wu, Yu; Liu, Y.; Yu, Peiping; Jia, Ran; Goddard, William A.; Cheng, Tao

doi:10.1016/j.mtener.2021.100730

Cited by 36 publications

(32 citation statements)

References 49 publications

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“…In the mixed solution, LiPF 6 would quickly decompose and release gaseous phosphorus pentafluoride (PF 5 ) and the PF 5 could trigger the cationic ringopening reactions of DOL. [41][42][43][44][45] Then, the PF 5 combined with a trace of water to form H + (PF 5 OH) − , which acted as the initiator that induced the insertion of oxygen ions into the ring-opening DOL monomer to trigger the growth of polymer chains. At the same time, LiTFSI worked as a catalyst that promoted the self-polymerization of DOL.…”

Section: Design and Synthesis Of Qse Filmsmentioning

confidence: 99%

Constructing Highly Conductive and Thermomechanical Stable Quasi‐Solid Electrolytes by Self‐Polymerization of Liquid Electrolytes within Porous Polyimide Nanofiber Films

Huang

Liu

Chen

et al. 2022

Adv Funct Materials

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Solid electrolytes are being considered as an effective solution to replace liquid ones for building safer batteries, but they suffer either low ionic conductivity or large contact ohmic impedance. Here, a highly conductive and thermomechanically stable quasi‐solid electrolytes (QSE) by self‐polymerization of a commercially available liquid electrolytes (1,3‐dioxolane (DOL), 1,2‐dimethoxyethane (DME), lithium trifluoromethane sulfonimide (LiTFSI) and LiPF6) at room temperature in a porous polyimide nanofiber film are reported. LiPF6 initiates the ring‐opening reaction of DOL and LiTFSI promotes the self‐polymerization to form poly‐DOL (PDOL), while the plasticizer of DME solidifies the PDOL. On the other hand, polyimide has a great affinity with PDOL that facilitates to form stable QSE network. As a result, the QSE film shows a high room‐temperature ionic conductivity of 2.9 × 10−3 S cm−1, a high mechanical strength of 31 MPa, and high heat resistance to 160 °C. The LiFePO4||QSE||Li batteries with a high cathode loading of ≈18.7 mg cm−2 show great cycling performance and stable electrode/electrolyte interfaces at a high current rate of 0.5 C with a capacity retention of 91.8% over 200 cycles at room temperature.

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Section: Design and Synthesis Of Qse Filmsmentioning

confidence: 99%

Constructing Highly Conductive and Thermomechanical Stable Quasi‐Solid Electrolytes by Self‐Polymerization of Liquid Electrolytes within Porous Polyimide Nanofiber Films

Huang

Liu

Chen

et al. 2022

Adv Funct Materials

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“…Recently, molecular dynamics (MD) simulations have been widely used as a promising tool to explore complex reactions at the atomic level, especially those based on DFT. 35 The computational cost of DFT-MD or ab initio MD (AIMD) from electronic structure computations is high, preventing the simulation from reaching a sufficient time scale. Instead, a force field (FF) that is based on empirical functional forms with a trained parameter has a significant advantage in computational efficiency, which has been widely employed to simulate the battery interface in extended time and size scales.…”

Section: T H Imentioning

confidence: 99%

Multiscale Simulation of Solid Electrolyte Interface Formation in Fluorinated Diluted Electrolytes with Lithium Anodes

Sun

Liu

et al. 2022

ACS Appl. Mater. Interfaces

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Lithium metal batteries (LMBs) hold great promise in facilitating high-energy batteries due to their merits such as high specific capacity, low reduction potential, and so forth. However, the realizations of practical LMBs are hindered by severe problems such as undesirable dendrite growth, poor Coulombic efficiency, and so forth. A recently proposed fluorinated electrolyte based on 1 M lithium bis(fluorosulfonyl)imide (LiFSI) dissolved in designed fluorinated 1,4-dimethoxybutane (FDMB) solvent has attracted significant attention because of its excellent electrochemical performance that origins from its superior physical and chemical properties, especially its unique ability in forming a robust, stable solid electrolyte interphase (SEI). However, the detailed structure and reaction mechanism of the SEI formation in such a novel electrolyte remains unclear. In this work, we carry out a hybrid ab initio and reactive molecular dynamics (HAIR) simulation to investigate the elementary reactions that regulate the formation of the primitive SEI, paying special attention to the process that involves FDMB, the fluorinated solvent. HAIR simulation reveals that both FSI − anion and FDMB provide F that is adequate to form a uniformed LiF layer that resembles the inorganic inner layer (IIL) of the SEI. N and S radicals from the FSI − anion, which do not deposit on the electrode interface to form lithium-containing inorganic substances, promote the polymerization reaction of unsaturated carbon chains produced by FDMB defluorination, forming the organic outer layer (OOL) of the SEI. The combination of the LiF-rich IIL and polymer-rich organic OOL explains the superior performance of the FDMB-based electrolyte in the device. The detailed reaction mechanism and SEI observed in this work provide insights into the atomic scale for the rational design of F-rich electrolytes in the near future.

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“…S1a †). 54 The long chain poly-DOL may crystallize and retard ion motion in the electrolyte. 55 By contrast, LiNO 3 does not initiate the ringopening polymerization of DOL but coordinates with DOL and LiPF 6 in the electrolyte, through the interactions of the electron-decient N atoms on LiNO 3 with DOL and LiPF 6 , to prevent extensive DOL polymerization.…”

Section: Characteristics Of Electrolytesmentioning

confidence: 99%

Ternary-salt gel polymer electrolyte for anode-free lithium metal batteries with an untreated Cu substrate

et al. 2022

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Pathway of in situ polymerization of 1,3-dioxolane in LiPF6 electrolyte on Li metal anode

Cited by 36 publications

References 49 publications

Constructing Highly Conductive and Thermomechanical Stable Quasi‐Solid Electrolytes by Self‐Polymerization of Liquid Electrolytes within Porous Polyimide Nanofiber Films

Constructing Highly Conductive and Thermomechanical Stable Quasi‐Solid Electrolytes by Self‐Polymerization of Liquid Electrolytes within Porous Polyimide Nanofiber Films

Multiscale Simulation of Solid Electrolyte Interface Formation in Fluorinated Diluted Electrolytes with Lithium Anodes

Ternary-salt gel polymer electrolyte for anode-free lithium metal batteries with an untreated Cu substrate

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