Characterization of Lithium Electrode in Lithium Imides/Ethylene Carbonate and Cyclic Ether Electrolytes

Ota, Hitoshi; Sakata, Yuuichi; Wang, Xianming; Sasahara, Jun; Yasukawa, Eiki

doi:10.1149/1.1644137

Cited by 112 publications

(112 citation statements)

References 42 publications

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“…The electrolytes have comparable ionic conductivities (11 mS cm −1 for LP30 [10] and 15 mS cm −1 for LiTFSI [11]), which implies that morphological differences are related to the different SEI compositions (containing e.g. Li x PF y in LP30 [12] and Li 2 SO 3 and Li 2 S in LiTFSI [13]). Characteristic differences in the growth morphology were identified: In contrast to LP30, spheres (marked by arrows in Fig.…”

Section: Resultsmentioning

confidence: 99%

Comparison of the growth of lithium filaments and dendrites under different conditions

Steiger

Richter

Wenk

et al. 2015

Electrochemistry Communications

110

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Section: Resultsmentioning

confidence: 99%

Comparison of the growth of lithium filaments and dendrites under different conditions

Steiger

Richter

Wenk

et al. 2015

Electrochemistry Communications

110

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“…28 ssNMR has also been applied to the study of carbonate-based electrolyte decomposition and of SEI composition. 7,[29][30][31][32][33][34][35][36][37][38][39] With these motivations, this work describes the use of 19 …”

mentioning

confidence: 99%

¹⁹F and³¹P Solid-State NMR Characterization of a Pyridine Pentafluorophosphate-Derived Solid-Electrolyte Interphase

Hall

Werner‐Zwanziger

Dahn

2017

J. Electrochem. Soc.

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Solid-state NMR spectroscopy was used to characterize the solid-electrolyte interphase (SEI) formed on the graphite electrode surface from the electrolyte additive pyridine pentafluorophosphate (PPF). The PPF-derived SEI was prepared in a full Li(Ni 0.4 Mn 0.4 Co 0.2 )O 2 /graphite cell, rather than in a coin cell or using a bench-top synthesis approach. 19 F and 19 F→ 31 P crosspolarization measurements provide direct evidence that F atoms and P-F bonds are present at the graphite surface. By comparing rinsed and unrinsed samples, an insoluble SEI component was differentiated from residual LiPF 6 from the dried electrolyte. The SEI species contains F and P chemical environments that are similar to, but distinct from, the additive starting material and the lithium hexaflurophosphate (LiPF 6 ) electrolyte salt used in this work. The results are consistent with the previously proposed formation of a dilithium 4,4'-bipyridine-N,N'-bis(pentafluorophosphate) salt. LiF was also observed and is attributed to decomposition of the PPF-derived surface layer and/or the LiPF 6 electrolyte salt. There is an increasing demand for longer-lasting and higher energy lithium-ion cells. Sacrificial electrolyte additives are a practical route to forming passive solid-electrolyte interphase (SEI) layers that limit electrolyte decomposition during cell storage and operation, which in turn can lead to improved cell performance and lifetime. [1][2][3] In recent years, significant steps have been made toward understanding the underlying chemistry of several electrolyte additives, including organic carbonate additives, 4-9 sulfur-containing additives, 6,10,11 and additives containing a Lewis acid-base adduct.6,12-14 Pyridine pentafluorophosphate (PPF, Figure 1a) belongs to this last category and has been shown to improve charge capacity retention after cycling at high temperature and high cell voltage.By combining several experimental techniques with density functional theory (DFT) calculations, a proposed pathway for SEI formation on the negative electrode from PPF has recently been proposed (Figure 1b). 13 It was suggested that during the formation cycle, dilithium 4,4'-bipyridine-N,N'-bis(pentafluorophosphate) salt, herein abbreviated as Li 2 (PPF) 2 , is produced and incorporated into the negative electrode SEI. However, the direct characterization of the PPF-derived SEI component(s) remains a significant challenge. This work explores the use of 19 F and 31 P solid-state nuclear magnetic resonance spectroscopy (ssNMR) as a complementary method to examine the chemical environment of the F and P atoms incorporated into the SEI.Whereas the sensitivity of ssNMR may be correctly anticipated to pose experimental challenges, the PPF additive is appealing because it is rich in both F and P atoms. These atoms are both desirable for the practical reasons of the high natural abundance of the NMR-active 19 F and 31 P isotopes (∼100%), their relatively high gyromagnetic ratios (γ 19F = 40.052 MHz T −1 , γ 31P = 17.235 MHz T −1 ), and because they ...

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“…8 are the various vibrational modes of CF 3 . 28 The bands due to m s (SNS) and m(CÀ ÀS) modes are at 776.7 and 768 cm 21 , respectively. The Figure 5(b) shows the various vibrational modes and characteristic infrared frequencies of PC along with the bands of LiBETI, the former has already been summarized by Battisti et al in more detail.…”

Section: Spectral Studiesmentioning

confidence: 98%

Nanocomposite polymer electrolytes by in situ polymerization of methyl methacrylate: For electrochemical applications

Ahmad

Agnihotry

Ahmad

2007

J of Applied Polymer Sci

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Hybrid materials, which combine properties of organic-inorganic materials, are of profound interest owing to their unexpected synergistically derived properties and are considered as innovative advanced materials promising new applications in many fields such as optics, electronics, ionics and mechanics. Inorganic fillers are added to polymers in order to increase some of the properties of the compounds. These hybrid polymeric materials are replacing the pristine polymers due to their higher strength and stiffness. In the present work, studies concerning the preparation of poly (methylmethacrylate) [PMMA] and the nanocomposites PMMA/SiO 2 , PMMA/TiO 2 are reported. These nanocomposite polymers were synthesized by means of free radical polymerization of methylmethacrylate, further ''solgel'' transformation-based hydrolysis and condensation of corresponding alkoxide was used to prepare the inorganic phase during the polymerization process of MMA. Electrolytes were synthesized based on these nanocomposite polymers and have shown superior properties as compared to conventional polymer electrolytes. The nanocomposites and the nanocomposite polymer electrolytes (NPEs) with different lithium salts were investigated through an array of techniques including FTIR and calorimetry along with the electrochemical and rheological techniques.

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Characterization of Lithium Electrode in Lithium Imides/Ethylene Carbonate and Cyclic Ether Electrolytes

Cited by 112 publications

References 42 publications

Comparison of the growth of lithium filaments and dendrites under different conditions

Comparison of the growth of lithium filaments and dendrites under different conditions

¹⁹F and³¹P Solid-State NMR Characterization of a Pyridine Pentafluorophosphate-Derived Solid-Electrolyte Interphase

Nanocomposite polymer electrolytes by in situ polymerization of methyl methacrylate: For electrochemical applications

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Characterization of Lithium Electrode in Lithium Imides/Ethylene Carbonate and Cyclic Ether Electrolytes

Cited by 112 publications

References 42 publications

Comparison of the growth of lithium filaments and dendrites under different conditions

Comparison of the growth of lithium filaments and dendrites under different conditions

19F and31P Solid-State NMR Characterization of a Pyridine Pentafluorophosphate-Derived Solid-Electrolyte Interphase

Nanocomposite polymer electrolytes by in situ polymerization of methyl methacrylate: For electrochemical applications

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¹⁹F and³¹P Solid-State NMR Characterization of a Pyridine Pentafluorophosphate-Derived Solid-Electrolyte Interphase