Raman and NMR analysis of LiClO4 concentrated solutions in ethylene carbonate-propylene carbonate

Cazzanelli, E.; Mustarelli, Piercarlo; Benevelli, Francesca; Appetecchi, Giovanni Battista; Croce, F.

doi:10.1016/0167-2738(96)00154-3

Cited by 38 publications

(43 citation statements)

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“…In a previous paper, 11 we have shown with Raman and 13 C NMR that a phase transition takes place at NХ0.5, where ''stable'' ͑in the second time scale͒ complexes are formed between a Li ϩ and two solvent molecules, preferably an EC and a PC. Now, our overall spectroscopic and calorimetric findings allow us to sketch the following tentative model for the cations solvation in the pseudobinary system LiClO 4 -͑ECϩPC͒:…”

Section: Discussionmentioning

confidence: 98%

“…In our previous paper 11 we showed that the conductivity displays a minimum vs salt concentration near NХ0.5. The compositions far from the critical concentration showed a well-defined Vogel-Tamman-Fulcher 13 behavior described by the equation…”

Section: Information From Conductivitymentioning

confidence: 97%

“…5,6,11,[17][18][19] In these studies, the most evident effect on the vibrational spectra of the solvents is the strong interaction of the ions with the ring breathing ( 7 ) of EC molecule and ring bending mode ( 8 ) of both the EC and PC species, which induces for the ''perturbed'' solvent molecules a frequency upshift of about 10 cm Ϫ1 with respect to the unperturbed ones. The recent IR study 14 has been performed on solutions of LiClO 4 in pure EC, up to 30% of electrolyte content, while the Raman study, 5 also performed using pure EC as solvent, concerned relatively low ͑up to 1 M͒ electrolyte concentration.…”

Section: A the Raman Informationmentioning

confidence: 99%

“…The first number corresponds to n EC Х2.8, while the second corresponds to n EC Хϭ1.4. By assuming that EC or PC molecules enter the solvation shell in the same ratio of their relative concentration in the solvent, nХ4 is obtained at low concentrations and nХ2 is obtained at the critical concentration, which are the solvation numbers found in dilute solutions, 5 and that associated to the sandwich configuration postulated for high electrolyte contents, 11 respectively. On the basis of Raman data and their fitting analysis, it is hard to discriminate between a continuous slope change ͑decreasing exponential function͒ or a two-slopes behavior ͑two straight lines with the slope change occurring at about N EC Х0.35͒.…”

Section: A the Raman Informationmentioning

confidence: 99%

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Li + solvation in ethylene carbonate–propylene carbonate concentrated solutions: A comprehensive model

Cazzanelli

Croce

Appetecchi

et al. 1997

The Journal of Chemical Physics

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Spectroscopic ͑Raman, NMR, impedance spectroscopy͒, and thermal ͓differential scanning calorimetry ͑DSC͔͒ techniques have been used to study the solvation mechanism of lithium ions in ethylene carbonate ͑EC͒-propylene carbonate ͑PC͒ concentrated solutions. For values of N ϭ͓Li ϩ ͔/͓ECϩPC͔р0.2 all the cations are solvated by ϳ4 solvent molecules and interaction chiefly takes place between Li ϩ and the ring oxygens. For NϾ0.2 a part of Li ϩ ions begins to form complexes with two solvent molecules ͑sandwich configuration͒. At NХ0.5 nearly all cations are complexed, and a crystalline compound is formed at room temperature. For higher values of N a reassociation of the salt takes place.

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Section: Discussionmentioning

confidence: 98%

Section: Information From Conductivitymentioning

confidence: 97%

Section: A the Raman Informationmentioning

confidence: 99%

Section: A the Raman Informationmentioning

confidence: 99%

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Li + solvation in ethylene carbonate–propylene carbonate concentrated solutions: A comprehensive model

Cazzanelli

Croce

Appetecchi

et al. 1997

The Journal of Chemical Physics

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“…Raman spectroscopy has been used to elucidate the solution structures of non-aqueous electrolyte for lithium-ion and magnesium batteries. 15,[21][22][23][24][25][26] The magnesium deposition behavior and solution structure of various mixed electrolytes have been compared. Results showing changes in the coordination structure by mixing EtMgBr and Mg(TFSA) 2 might provide information to facilitate the design of electrolyte systems for magnesium secondary batteries.…”

Section: Introductionmentioning

confidence: 99%

Solution Structure and Magnesium Deposition Electrochemistry of Mixing Alkylmagnesium Halide with Magnesium Sulfonyl Amide/Glyme Solution

Egashira

Hiratsuka

2016

Electrochemistry

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To elucidate effective species and their quantitative requirements for reversible magnesium deposition, a triglyme solution of ethylmagnesium bromide (EtMgBr) complex was mixed with magnesium bis(trifluoromethanesulfonyl) amide/triglyme solution in various ratios. The mixed electrolyte characteristics have been assessed using electrochemical magnesium deposition tests, titration of methanol, and Raman spectroscopy. The existence of EtMgBr reduces the overpotential of magnesium deposition. The Coulombic efficiency of this process varies linearly with the EtMgBr content, although the active EtMgBr decreases more than expected from the mixing ratio. Raman spectra for the mixed electrolyte suggest a change in the structure of magnesium bromide species and coordination mode of magnesium by mixing of EtMgBr with magnesium sulfonylamide salt.

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Sustained Release‐Driven Formation of Ultrastable SEI between Li₆PS₅Cl and Lithium Anode for Sulfide‐Based Solid‐State Batteries

Sun

et al. 2020

Advanced Energy Materials

114

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considerable advantages are mainly associated with the cooperation of high theoretical capacity (3860 mAh g −1), low density (0.53 g cm −3), and the lowest reduction potential (−3.04 V vs standard hydrogen electrode) of Li anode and the non-flammability, absence of leakage and vaporization of inorganic solid-state electrolytes (SEs). [1b,2] Nevertheless, the unfavorable conductivity of SEs and the large interfacial resistance between Li anode and SEs make it difficult to realize practical application for SSMLBs. Latterly, the sulfide-type solid electrolytes (SSEs), such as Li 10 GeP 2 S 12 , [3] Li 7 P 3 S 11 , [4] and Li 6 PS 5 Cl [5] have attracted widespread concerns due to their outstanding ionic conductivity (>1.0 mS cm −1 at ambient temperature), which holds the promise for providing the potential application in SSLMBs. [6] Unfortunately, the poor compatibility between SSEs and Li anode has been proven theoretically [7] and experimentally, [8] leading to the increase of interfacial resistance and the formation of Li dendrite through the grain boundary or voids in SSEs. [9] In response to this, several strategies have been carried out in SSLMBs as below: i) The doping of element into SSEs can availably modulate their own surface energy to provide a better protection for Li metal, which is conductive to improving its electrochemical stability. [9b,10] ii) Li-M alloys The sulfide-type solid electrolyte (SSE) is considered a promising candidate for solid-state lithium metal batteries (SSLMBs) owing to its advantages of superior ionic conductivity. Nevertheless, the incompatibility of the sulfide and lithium metal can result in undesirable interface resistance and rapid Li dendrite growth, which seriously hinders its commercial applications. Herein, inspired by the moderation and long duration of sustained release drug carriers when combined with active pharmaceutical ingredients in the biomedical field, poly (propylene carbonate) (PPC) and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) gradually interact with a Li anode with constantly decreased Li/SSE interfacial resistance. In addition to intimate contact, the ultrastable LiF-enriched solid electrolyte interphase (SEI) is in situ formed via a sustained release effect, which suppresses the Li dendrite effectively. As a result, the symmetric cells demonstrate stable cycling performance for 1200 h at a current density of 0.1 mA cm −2 and 300 h at 0.5 mA cm −2. Moreover, LiFePO 4 / Li 6 PS 5 Cl /Li SSLMB delivers a high discharge capacity of over 132.8 mAh g −1 for 900 cycles at 1C with steady Coulombic efficiency. Therefore, this sustained release mechanism and its initially successful application in interfacial modification increase the potential for commercial applications of SSLMBs.

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Raman and NMR analysis of LiClO4 concentrated solutions in ethylene carbonate-propylene carbonate

Cited by 38 publications

References 9 publications

Li + solvation in ethylene carbonate–propylene carbonate concentrated solutions: A comprehensive model

Li + solvation in ethylene carbonate–propylene carbonate concentrated solutions: A comprehensive model

Solution Structure and Magnesium Deposition Electrochemistry of Mixing Alkylmagnesium Halide with Magnesium Sulfonyl Amide/Glyme Solution

Sustained Release‐Driven Formation of Ultrastable SEI between Li₆PS₅Cl and Lithium Anode for Sulfide‐Based Solid‐State Batteries

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Raman and NMR analysis of LiClO4 concentrated solutions in ethylene carbonate-propylene carbonate

Cited by 38 publications

References 9 publications

Li + solvation in ethylene carbonate–propylene carbonate concentrated solutions: A comprehensive model

Li + solvation in ethylene carbonate–propylene carbonate concentrated solutions: A comprehensive model

Solution Structure and Magnesium Deposition Electrochemistry of Mixing Alkylmagnesium Halide with Magnesium Sulfonyl Amide/Glyme Solution

Sustained Release‐Driven Formation of Ultrastable SEI between Li6PS5Cl and Lithium Anode for Sulfide‐Based Solid‐State Batteries

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Sustained Release‐Driven Formation of Ultrastable SEI between Li₆PS₅Cl and Lithium Anode for Sulfide‐Based Solid‐State Batteries