Polypropylene carbonate-based electrolytes as model for a different approach towards improved ion transport properties for novel electrolytes

Gerlitz, Anna Isabella; Diddens, Diddo; Grünebaum, Mariano; Heuer, Andreas; Winter, Martin; Wiemhöfer, Hans‐Dieter

doi:10.1039/d2cp03756d

Cited by 10 publications

(3 citation statements)

References 88 publications

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“…The peak associated with the free C═O in PCL centered at 1722 cm −1 undergoes a progressive shifting to 1718 cm −1 with the successive incorporation of LiFSI and LLZTO due to the multiple intermolecular coordination of C═O⋯Li + and C═O⋯LLZTO. [ 27 ] In addition, the peak corresponding to S═O of FSI − anions at 1245 cm −1 exhibits a downshift to 1237 cm −1 with the introduction of LLZTO nanoparticles owing to the S═O⋯LLZTO intermolecular coordination (Figure S7, Supporting Information). To confirm the above working principle, we have also conducted coordination interaction tests between LLZTO nanoparticles and other carbonyl‐containing polymer electrolytes, including polyethylene carbonate (PEC, polycarbonate) and polymethyl methacrylate (PMMA, polyester).…”

Section: Resultsmentioning

confidence: 99%

Insight into Multiple Intermolecular Coordination of Composite Solid Electrolytes via Cryo‐Electron Microscopy for High‐Voltage All‐Solid‐State Lithium Metal Batteries

Wang,

Xu,

Fan

et al. 2024

Advanced Materials

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Polymer/ceramic‐based composite solid electrolytes (CSE) are promising candidates for all‐solid‐state lithium metal batteries (SLBs), benefiting from the combined mechanical robustness of polymeric electrolytes and the high ionic conductivity of ceramic electrolytes. However, the interfacial instability and poorly understood interphases of CSE hinder their application in high‐voltage SLBs. Herein, we discover a simple but effective CSE that stabilizes high‐voltage SLBs by forming multiple intermolecular coordination interactions between polyester and ceramic electrolytes. The multiple coordination between the carbonyl groups in poly(ε‐caprolactone) and the fluorosulfonyl groups in anions with Li6.5La3Zr1.5Ta0.5O12 nanoparticles is directly visualized by cryogenic transmission electron microscopy and further confirmed by theoretical calculation. Importantly, the multiple coordination in CSE not only prevents the continuous decomposition of polymer skeleton by shielding the vulnerable carbonyl sites but also establishes stable inorganic‐rich interphases through preferential decomposition of anions. The stable CSE and its inorganic‐rich interphases enable Li||Li symmetric cells with an exceptional lifespan of over 4800 hours without dendritic shorting at 0.1 mA cm−2. Moreover, the high‐voltage SLB with LiNi0.5Co0.2Mn0.3O2 cathode displays excellent cycling stability over 1100 cycles at a 1C charge/discharge rate. This work reveals the underlying mechanism behind the excellent stability of coordinating composite electrolytes and interfaces in high‐voltage SLBs.This article is protected by copyright. All rights reserved

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Section: Resultsmentioning

confidence: 99%

Insight into Multiple Intermolecular Coordination of Composite Solid Electrolytes via Cryo‐Electron Microscopy for High‐Voltage All‐Solid‐State Lithium Metal Batteries

Wang,

Xu,

Fan

et al. 2024

Advanced Materials

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“…Considerable advantages were found for water-in-salt electrolytes (WISE) compared with the commercial organic electrolytes after introduced by Suo and his colleagues: nonflammable, nonvolatile, low toxicity, and wider electrochemical window. − Following this premier work, a fair amount of studies with multiple advanced techniques, such as Raman spectroscopy and infrared spectroscopy (IR), have been reported to explore the solvation structure of the WISE. − The anion coordination mode for imide-based electrolyte was commonly investigated by deconvoluting the Raman peak (S–N–S bending vibration) into three bands, which correspond to solvent-separated ion pair (SSIP), contact ion pair (CIP), and aggregate (AGG), respectively. − By analyzing the shift of infrared peaks caused by the vibration of the hydrogen–oxygen bond or deuterium-oxygen bond, the bulk-like and ion-bound water were found to coexist in the system and serve different roles as a medium for lithium ion transport and a lubricant, respectively. ,,, …”

Section: Introductionmentioning

confidence: 99%

Solvation Structure of Methanol-in-Salt Electrolyte Revealed by Small-Angle X-ray Scattering and Simulations

Lyu,

Wang,

Liu

et al. 2024

ACS Nano

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The solvation structure of water-in-salt electrolytes was thoroughly studied, and two competing structures�anion solvated structure and anion network� were well-defined in recent publications. To further reveal the solvation structure in those highly concentrated electrolytes, particularly the influence of solvent, methanol was chosen as the solvent for this proposed study. In this work, small-angle X-ray scattering, small-angle neutron scattering, Fourier-transform infrared spectroscopy, and Raman spectroscopy were utilized to obtain the global and local structural information. With the concentration increment, the anion network formed by TFSI − became the dominant structure. Meanwhile, the hydrogen bonds among methanol were interrupted by the TFSI − anion and formed a new connection with them. Molecular dynamic simulations with two different force fields (GAFF and OPLS-AA) are tested, and GAFF agreed with synchrotron small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) results well and provided insightful information about molecular/ion scale solvation structure. This article not only deepens the understanding of the solvation structure in highly concentrated solutions, but more importantly, it provides additional strong evidence for utilizing SAXS/WAXS to validate molecular dynamics simulations.

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“…These properties measure the effectiveness of ILEs as an electrolyte in batteries. Experimentally, the collective salt diffusion coefficient can be determined using the confined diffusion method and the individual ion diffusion coefficient can be obtained using the pulsed field gradient nuclear magnetic resonance (PFG-NMR) [14,15]. The ionic conductivity is typically measured through alternating current impedance spectroscopy with a small applied voltage (∼10 mV) [16][17][18].…”

Section: Introductionmentioning

confidence: 99%

Ion correlations in quaternary ionic liquids electrolytes

Tong,

Liang,

von Solms

et al. 2024

J. Phys. Mater.

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Lithium-ion batteries are currently the most popular and widely used energy storage devices, almost omnipresent within modern society in portable devices, electrical vehicles, energy storage stations, and so on. The demand for more efficient, more durable, and more sustainable batteries is rapidly growing. The electrolyte is a key element to improve the performance of lithium-ion batteries. In this work, we focus on quaternary ionic liquid electrolyte (ILE), which uses a four-component ionic liquid as the solvent. Quaternary ILE has found wide applications in energy storage systems, but the ion transport in the electrolyte has not been fully characterized to provide the best strategy for performance optimisation. In this work, we systematically analyse the ion transport in the quaternary ILE and uncover how the correlations between various ions affect the conductivity of the electrolyte. We have found that lithium ions are transported in charge clusters, leading to a negative effective transference number of lithium ions. Furthermore, we identify the stable cluster conformations in ILE by cluster analysis and quantum chemical computing. This work highlights the necessity of considering ion correlations in multi-component electrolyte systems.

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Polypropylene carbonate-based electrolytes as model for a different approach towards improved ion transport properties for novel electrolytes

Abstract: Linear poly(alkylene carbonates) such as polyethylene carbonate (PEC) and polypropylene carbonate (PPC) have gained increasing interest due to their remarkable ion transport properties such as high Li+ transference numbers. The...

Cited by 10 publications

References 88 publications

Insight into Multiple Intermolecular Coordination of Composite Solid Electrolytes via Cryo‐Electron Microscopy for High‐Voltage All‐Solid‐State Lithium Metal Batteries

Insight into Multiple Intermolecular Coordination of Composite Solid Electrolytes via Cryo‐Electron Microscopy for High‐Voltage All‐Solid‐State Lithium Metal Batteries

Solvation Structure of Methanol-in-Salt Electrolyte Revealed by Small-Angle X-ray Scattering and Simulations

Ion correlations in quaternary ionic liquids electrolytes

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