Effect of Fluoroethylene Carbonate (FEC) on the Performance and Surface Chemistry of Si-Nanowire Li-Ion Battery Anodes

Etacheri, Vinodkumar; Haik, Ortal; Goffer, Yossi; Roberts, G. A.; Stefan, Ionel C.; Fasching, Rainier; Aurbach, Doron

doi:10.1021/la203712s

Cited by 720 publications

(936 citation statements)

References 60 publications

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“…For the NaNi 0.35 Mn 0.35 Fe 0.3 O 2 cathodes, both F1s spectra in electrolyte with or without FEC have a distinct peak at 687.7 eV (Figure 5c), corresponding to some organic fluorides from PDVF binder. It is noticed a new peak appears at 687.7 eV in FEC‐containing electrolyte, probably can be attributed to NaF 67. This phenomenon indicates that FEC decomposition also contributes to the SEI formation on the cathode.…”

Section: Resultsmentioning

confidence: 89%

“…In order to avoid the confusion of the resource of F signal, NaPF 6 is replaced by NaClO 4 , which has no adverse effect on the electrochemical performance of the two materials. As can be seen in Figure 5a, the F1s spectra of the Sb anode cycled in the FEC‐free TMP electrolyte show no F signal at all, while the spectra in the FEC‐containing TMP electrolyte has a distinct peak at 686.8 eV and a small bulge at 683.4 eV, corresponding to some kinds of organic fluorides and NaF, respectively 64, 66, 67. Thus, the XPS spectra clearly demonstrate the SEI formation on the Sb surface by FEC decomposition.…”

Section: Resultsmentioning

confidence: 98%

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A Safer Sodium‐Ion Battery Based on Nonflammable Organic Phosphate Electrolyte

et al. 2016

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Sodium‐ion batteries are now considered as a low‐cost alternative to lithium‐ion technologies for large‐scale energy storage applications; however, their safety is still a matter of great concern for practical applications. In this paper, a safer sodium‐ion battery is proposed by introducing a nonflammable phosphate electrolyte (trimethyl phosphate, TMP) coupled with NaNi0.35Mn0.35Fe0.3O2 cathode and Sb‐based alloy anode. The physical and electrochemical compatibilities of the TMP electrolyte are investigated by igniting, ionic conductivity, cyclic voltammetry, and charge–discharge measurements. The results exhibit that the TMP electrolyte with FEC additive is completely nonflammable and has wide electrochemical window (0–4.5 V vs. Na/Na+), in which both the Sb‐based anode and NaNi0.35Mn0.35Fe0.3O2 cathode show high reversible capacity and cycling stability, similarly as in carbonate electrolyte. Based on these results, a nonflammable sodium‐ion battery is constructed by use of Sb anode, NaNi0.35Mn0.35Fe0.3O2 cathode, and TMP + 10 vol% FEC electrolyte, which works very well with considerable capacity and cyclability, demonstrating a promising prospect to build safer sodium‐ion batteries for large‐scale energy storage applications.

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Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 98%

A Safer Sodium‐Ion Battery Based on Nonflammable Organic Phosphate Electrolyte

et al. 2016

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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%

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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“…Further extending the cycle life of Si anodes also relies on forming a stable SEI that must be sustained throughout cycling. Fluorinated ethylene carbonate (FEC) has been employed as an additive to form a more robust SEI, 162 but the jury is still out as it is likely consumed during cycling, resulting in long-term capacity fade. 163 Despite significant progress, many challenges remain unsolved such as cycle life.…”

Section: High-voltage Cathode Materialsmentioning

confidence: 99%

Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries

Ruther

et al. 2017

JOM

228

136

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Reducing cost and increasing energy density are two barriers for widespread application of lithium-ion batteries in electric vehicles. Although the cost of electric vehicle batteries has been reduced by $70% from 2008 to 2015, the current battery pack cost ($268/kWh in 2015) is still >2 times what the USABC targets ($125/kWh). Even though many advancements in cell chemistry have been realized since the lithium-ion battery was first commercialized in 1991, few major breakthroughs have occurred in the past decade. Therefore, future cost reduction will rely on cell manufacturing and broader market acceptance. This article discusses three major aspects for cost reduction: (1) quality control to minimize scrap rate in cell manufacturing; (2) novel electrode processing and engineering to reduce processing cost and increase energy density and throughputs; and (3) material development and optimization for lithium-ion batteries with high-energy density. Insights on increasing energy and power densities of lithium-ion batteries are also addressed.

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Effect of Fluoroethylene Carbonate (FEC) on the Performance and Surface Chemistry of Si-Nanowire Li-Ion Battery Anodes

Cited by 720 publications

References 60 publications

A Safer Sodium‐Ion Battery Based on Nonflammable Organic Phosphate Electrolyte

A Safer Sodium‐Ion Battery Based on Nonflammable Organic Phosphate Electrolyte

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

Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries

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