Investigation of the Solid Electrolyte Interphase Formed by Fluoroethylene Carbonate on Si Electrodes

Nakai, Hiroyuki; Kubota, T.; Kita, Akinori; Kawashima, Atsumichi

doi:10.1149/1.3589300

Cited by 326 publications

(427 citation statements)

References 16 publications

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“…As electrolyte solution, we use LP57 + 5 wt% fluoroethylene carbonate (FEC), as this additive is known to improve the capacity retention of silicon-based electrodes. [19][20][21][22][23][24][25] The capacity retention and the coulombic efficiency of the LNMO/SiG cells with 5 wt% (green symbols) and without lithium oxalate (black symbols) in the cathode are shown in Figures 4a and 4b, respectively. The first charge capacities are 145 mAh/g LNMO for cells without lithium oxalate and 173 mAh/g LNMO for cells with 5 wt% lithium oxalate (open symbols), similar to the corresponding cells with graphite anodes.…”

Section: Resultsmentioning

confidence: 99%

“…FEC consumption in LNMO/SiG full cells with and without lithium oxalate.-To understand to which extent CO 2 participates in SEI formation when FEC is present, we conducted a post-mortem analysis of the electrolyte solution of aged LNMO/SiG cells without lithium oxalate and with 5 wt% lithium oxalate after 50 and 250 cycles, quantifying the amount of residual FEC by 19 F-NMR (for more details see Jung et al 22 ). The upper x-axis of Figure 5 shows the amount of residual FEC found in the electrolyte solution.…”

Section: Resultsmentioning

confidence: 99%

“…In contrast to FEC, where the consumed amount can be easily determined by 19 F-NMR, a quantification of the remaining CO 2 after extended cycling is not easily possible from the coin cells used in this study. However, Krause et al 18 showed that once all added CO 2 is consumed, Si alloy-based cells suffer from a severe drop in coulombic efficiency and capacity retention, analogously to what both Jung et al 22 and Petibon et al 24 demonstrated for the complete consumption of FEC from Si-based cells.…”

Section: Resultsmentioning

confidence: 99%

“…FEC quantification by NMR.-The consumption of fluoroethylene carbonate (FEC) during cycling of LNMO/SiG cells with and without lithium oxalate was investigated by 19 F-NMR of the recovered electrolyte solutions from full-cells. To this purpose, LNMO/SiG full-cells with or without lithium oxalate and LP57 + 5 wt% FEC were cycled as described above, and carefully disassembled after 50 cycles or 250 cycles.…”

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Lithium Oxalate as Capacity and Cycle-Life Enhancer in LNMO/Graphite and LNMO/SiG Full Cells

Solchenbach

Wetjen

Pritzl

et al. 2018

J. Electrochem. Soc.

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In the present study, we explore the use of lithium oxalate as a "sacrificial salt" in combination with lithium nickel manganese spinel (LNMO) cathodes. By online electrochemical mass spectrometry (OEMS), we demonstrate that the oxidation of lithium oxalate to CO 2 (corresponding to 525 mAh/g) occurs quantitatively around 4.7 V vs. Li/Li + . LNMO/graphite cells containing 2.5 or 5 wt% lithium oxalate show an up to ∼11% higher initial discharge capacity and less capacity fade over 300 cycles (12% and 8% vs. 19%) compared to cells without lithium oxalate. In LNMO/SiG full-cells with an FEC-containing electrolyte solution, lithium oxalate leads to a better capacity retention (45% vs 20% after 250 cycles) and a higher coulombic efficiency throughout cycling (∼1%) compared to cells without lithium oxalate. When CO 2 from lithium oxalate oxidation is removed after formation, a similar capacity fading as in LNMO/SiG cells without lithium oxalate is observed. Hence, we attribute the improved cycling performance to the presence of CO 2 in the cells. Further analysis (e.g., FEC consumption by 19 F-NMR) indicate that CO 2 is an effective SEI-forming additive for SiG anodes, and that a combination of FEC and CO 2 has a synergistic effect on the lifetime of full-cells with SiG anodes. Lithium nickel manganese spinel (LiNi 0.5 Mn 1.5 O 4 , LNMO) is a promising cathode material for high energy lithium ion batteries due to its high operating potential around 4.7 V vs. Li/Li + , its high rate capability, structural stability and the absence of cobalt. However, its lower specific capacity (146 mAh/g LNMO ) compared to layered oxide materials (e.g. lithium nickel manganese cobalt oxide (NMC), specific capacity 150-250 mAh/g NMC ) 1 is regarded as a major drawback. In full-cells, the practically achievable capacity of LNMO is even lower, as the formation of the solid-electrolyte interphase (SEI) on the graphite anode consumes active lithium. For many layered oxide cathodes, however, the first cycle irreversible capacity of the cathode is similar to the capacity needed for SEI formation (∼20 mAh/g NMC ), and hence the practical discharge capacity of the cathode and the remaining active lithium are more or less balanced again. 2,3 In contrast, the first cycle irreversible capacity of LNMO (∼6 mAh/g LNMO ) is much lower than the capacity needed for SEI formation. This leads to a mismatch between active lithium and practical cathode capacity, i.e., there is not enough active lithium available to fully discharge the LNMO cathode during subsequent cycling.In cells with silicon-based anodes, active lithium losses on the anode are even higher compared to graphite, as the expansion of the silicon particles during the first lithiation leads to a continuous exposure of fresh, unpassivated silicon surface. 4 On this new surface, electrolyte reduction occurs instantaneously, which reduces the total lithium reservoir in the cell. Therefore, different ideas to increase the amount of active lithium in lithium ion full-cells have been suggested, ...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

See 2 more Smart Citations

Lithium Oxalate as Capacity and Cycle-Life Enhancer in LNMO/Graphite and LNMO/SiG Full Cells

Solchenbach

Wetjen

Pritzl

et al. 2018

J. Electrochem. Soc.

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“…A lot of work has been done to understand the SEI on graphitic negative electrodes while the field of SEI formation on silicon is still a young area with only a rather small number of publications. [4,[7][8][9][10][11][12][13][14][15][16][17][18][19] Philippe et al have…”

Section: Introductionmentioning

confidence: 99%

A hard X-ray photoelectron spectroscopy study on the solid electrolyte interphase of a lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide based electrolyte for Si-electrodes

Lindgren

Maibach

et al. 2016

Journal of Power Sources

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A High‐Energy Li‐Ion Battery Using a Silicon‐Based Anode and a Nano‐Structured Layered Composite Cathode

Chae

Noh

Lee

et al. 2014

Adv Funct Materials

142

102

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High capacity electrodes based on a Si composite anode and a layered composite oxide cathode, Ni‐rich Li[Ni0.75Co0.1Mn0.15]O2, are evaluated and combined to fabricate a high energy lithium ion battery. The Si composite anode, Si/C‐IWGS (internally wired with graphene sheets), is prepared by a scalable sol–gel process. The Si/C‐IWGS anode delivers a high capacity of >800 mAh g−1 with an excellent cycling stability of up to 200 cycles, mainly due to the small amount of graphene (∼6 wt%). The cathode (Li[Ni0.75Co0.1Mn0.15]O2) is structurally optimized (Ni‐rich core and a Ni‐depleted shell with a continuous concentration gradient between the core and shell, i.e., a full concentration gradient, FCG, cathode) so as to deliver a high capacity (>200 mAh g−1) with excellent stability at high voltage (∼4.3 V). A novel lithium ion battery system based on the Si/C‐IWGS anode and FCG cathode successfully demonstrates a high energy density (240 Wh kg−1 at least) as well as an unprecedented excellent cycling stability of up to 750 cycles between 2.7 and 4.2 V at 1C. As a result, the novel battery system is an attractive candidate for energy storage applications demanding a high energy density and long cycle life.

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Investigation of the Solid Electrolyte Interphase Formed by Fluoroethylene Carbonate on Si Electrodes

Cited by 326 publications

References 16 publications

Lithium Oxalate as Capacity and Cycle-Life Enhancer in LNMO/Graphite and LNMO/SiG Full Cells

Lithium Oxalate as Capacity and Cycle-Life Enhancer in LNMO/Graphite and LNMO/SiG Full Cells

A hard X-ray photoelectron spectroscopy study on the solid electrolyte interphase of a lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide based electrolyte for Si-electrodes

A High‐Energy Li‐Ion Battery Using a Silicon‐Based Anode and a Nano‐Structured Layered Composite Cathode

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