Enhancing Electrochemical Performance of Silicon Film Anode by Vinylene Carbonate Electrolyte Additive

Chen, Libao; Wang, Ke; Xie, Xiaohua; Xie, Jun

doi:10.1149/1.2338771

Cited by 110 publications

(114 citation statements)

References 18 publications

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“…15,[19][20][21] There have been claims in the literature that LiF is central to FEC's benefit, 15,21 which would suggest F-containing additives as beneficial to Si cycling. On the other hand VC is also seen as beneficial to Si cycling and does not contain any F. 22 In screenings of electrolyte additives, VC was shown to lead to considerable gassing with ongoing cycling 23 and CO 2 is part of proposed decomposition routes. 20 FEC can also lead to gassing particularly at high temperatures with CO 2 as the main component.…”

Section: Discussionmentioning

confidence: 99%

The Effect of Carbon Dioxide on the Cycle Life and Electrolyte Stability of Li-Ion Full Cells Containing Silicon Alloy

Krause

Chevrier

Jensen

et al. 2017

J. Electrochem. Soc.

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Carbon dioxide is shown to be an effective additive to standard Li-ion electrolyte for extending the cycle life of full pouch cells containing an engineered silicon alloy. CO 2 was introduced to pouch cells by adding a few milligrams of dry ice to cells before sealing. The cells contained composite negative electrodes formulated with 15 to 17 wt% of an engineered silicon alloy and a LiCoO 2 positive electrode. Parasitic electrolyte reactions were measured in-situ by isothermal micro-calorimetry and high precision coulometry and compared to cells containing 1-fluoro ethylene carbonate (FEC). Extended cycling of cells containing CO 2 were compared to cells containing FEC. Cell gas generation and gas consumption were measured by applying the Archimedes principle. A new approach using small tubes in pouch cells to differentiate volume changes from gassing and solid expansion is introduced. Cells with CO 2 showed significantly lower parasitic thermal power, improved coulombic efficiency and better capacity retention compared to cells containing electrolytes with FEC. The gas generation/consumption experiments showed that Si alloy reacts with CO 2 during cycling until it is fully consumed. Combining FEC and CO 2 reduces the consumption rate of CO 2 . Microscopy of cross-sectioned cycled electrodes showed a thin SEI layer and minimal silicon alloy erosion. The combined work establishes CO 2 as a powerful precursor to an effective SEI layer on silicon alloys. Finally, CO 2 is shown to be an effective SEI former for graphite in EC-free electrolytes. The desire to increase energy density in Li-ion cells has fueled the research and development of silicon and silicon-based materials as a component of Li-ion negative electrodes. In most cases, however, only small amounts of silicon or silicon alloy are used largely because of the generally inferior cycle life of silicon compared to graphite. While there can be several reasons for the inferior cycle life of silicon and silicon alloys one important contributor to poor cycle life is the erosion of the silicon particle by parasitic electrolyte reactions. [1][2][3] Because of the volume changes Si experiences during cycling, continuous passivation is required at the surface and the demands on the electrolyte system are greater than for graphite.Carbon dioxide (CO 2 ) has been described as an effective electrolyte additive in metallic Li cells many years ago. 4 In that work it was shown that cycling efficiencies of the Li electrode were greatly increased in the presence of CO 2 . With the development of Li-ion cell chemistry the use of CO 2 was also explored early on. [5][6][7] In a few papers on the subject it was shown that the CO 2 generators, known as pyrocarbonates, were effective in forming SEI layers on graphite. 8,9 More recently a patent by workers at Sanyo has described the effect of electrolytes containing CO 2 on the cycle life of sintered negative electrodes containing silicon. 10In the course of our work on the erosion of silicon alloys our interest was drawn to the ...

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Section: Discussionmentioning

confidence: 99%

The Effect of Carbon Dioxide on the Cycle Life and Electrolyte Stability of Li-Ion Full Cells Containing Silicon Alloy

Krause

Chevrier

Jensen

et al. 2017

J. Electrochem. Soc.

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“…[7][8][9][10][11][12][13][14][15][16][17][18][19][20] Diesen Problemen sollte durch eine Verringerung der Partikelgröße begegnet werden. [7, 8a,b] Hierzu wurden dünne Filme auf Siliciumbasis oder Siliciumlegierungen, [9,10,20] Siliciumdispersionen (in einer aktiven oder inaktiven Matrix) [11][12][13][14][15][16][17][18][19] oder eine Kohlenstoffbeschichtung sowie verschiedene Elektrolytsysteme eingesetzt. [15,20] Viele Gemische aus aktiven und inaktiven Komponenten wurden getestet, wobei die inaktive Komponente die Rolle eines strukturellen Puffers über-nimmt, der die großen Volumenänderungen des aktiven Silicium auffängt und den Verschleiß der Elektroden verringert.…”

unclassified

“…[7, 8a,b] Hierzu wurden dünne Filme auf Siliciumbasis oder Siliciumlegierungen, [9,10,20] Siliciumdispersionen (in einer aktiven oder inaktiven Matrix) [11][12][13][14][15][16][17][18][19] oder eine Kohlenstoffbeschichtung sowie verschiedene Elektrolytsysteme eingesetzt. [15,20] Viele Gemische aus aktiven und inaktiven Komponenten wurden getestet, wobei die inaktive Komponente die Rolle eines strukturellen Puffers über-nimmt, der die großen Volumenänderungen des aktiven Silicium auffängt und den Verschleiß der Elektroden verringert. [11][12][13][14][15][16][17][18][19] [21] Nach einem vereinfachten Reaktionsmechanismus für die Bildung von Kohlenstoffstrukturen wird im ersten Schritt das Kohlenhydrat dehydratisiert, und die dabei entstehenden organischen Verbindungen werden im zweiten Schritt polymerisiert und anschließend carbonisiert.…”

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Ein Si@SiO_x/C‐Nanokomposit als Anodenmaterial für Lithiumionenbatterien mit hoher Speicherleistung

Demir‐Cakan

Titirici

et al. 2008

Angewandte Chemie

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“…17 Since the amount and the thickness of the solid-electrolyte interphase (SEI) increase, the electrode resistance also increases signifcantly. 18 Since the pulverization of large-size Si particles such as μm-Si is essentially inevitable, electrolyte additives must be applied to form an effective SEI to suppress electrolyte decomposition. 16 Vinylene carbonate (VC) and fluoroethylene carbonate (FEC) have already been reported to be effective to improve cycle stability of Si thinfilm electrode.…”

mentioning

confidence: 99%

“…16 Vinylene carbonate (VC) and fluoroethylene carbonate (FEC) have already been reported to be effective to improve cycle stability of Si thinfilm electrode. 18,19 In this work, we investigated the effect of these electrolyte additives on μm-Si electrode prepared with a PI binder (PI-Si electrode). An effective electrolyte additive was also applied to the electrode from a μm-Si and soft carbon (SC) composite with a PI binder (PI-Si-SC electrode).…”

mentioning

confidence: 99%

Effect of Electrolyte Additives on Non-Nano-Si Negative Electrodes Prepared with Polyimide Binder

Uchida

Yamagata

Ishikawa

2014

J. Electrochem. Soc.

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We investigated the effect of electrolyte additives on an untreated, conventional micro-sized (non-nano) Si electrode prepared with a polyimide (PI) binder (PI-Si electrode). Both additives, vinylene carbonate (VC) and fluoroethylene carbonate (FEC), improved the cycle stability of a PI-Si electrode half-cell. The solid-electrolyte interphase (SEI) formed by FEC includes a large amount of LiF and shows quite low resistance. This SEI effectively suppresses electrolyte decomposition, and an electrolyte containing VC mainly forms a SEI with organic components, and shows a smaller suppression effect on the electrolyte's excessive decomposition. From the AC impedance measurement and SEM observation results, we found that the formation of a massive SEI prevents contacts among Si particles and increases the charge-transfer resistance of the PI-Si electrode. The applied FEC suppresses the revolution of this resistance, meaning that FEC functions as an electrolyte additive suitable for PI-Si electrodes. A PI, Si, and soft-carbon composite (PI-Si-SC) electrode half-cell shows excellent cycle stability and rate performance by an adjusted amount of FEC (10 wt%). A full-cell, which includes a LiNi 1/3 Mn 1/3 Co 1/3 O 2 positive electrode, the PI-Si-SC negative electrode, and the electrolyte containing 10 wt% FEC, also exhibits quite good cycle stability. Since high energy-density Li-ion batteries (LIBs) are attractive in various fields, applications for them continue to expand. Advanced electric vehicles and power storage systems for renewable energy require the enhanced performance of LIBs with higher power, energy density, and more safety. The rapid development of such mobile electronic devices as smartphones, tablets, and thin laptops has also significantly increased power consumption, requiring higher capacity LIBs.The energy density of LIBs has been greatly improved by enhancing electrode density and efficient packaging of each component into a cell. However, electrode active materials are basically unchanged from the beginning of LIB history; LiCoO 2 1 and LiMn 2 O 4 2 are used as a positive electrode, and graphite 3 is generally applied to a negative electrode. To meet demands to further improve energy density, next-generation LIBs require enhanced capacity based on an active material. However, it is difficult to increase the weight-based specific capacity of a positive electrode because such a "heavy" transition metal as a positive electrode material must increase the redox electrons and its redox potential.

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Enhancing Electrochemical Performance of Silicon Film Anode by Vinylene Carbonate Electrolyte Additive

Cited by 110 publications

References 18 publications

The Effect of Carbon Dioxide on the Cycle Life and Electrolyte Stability of Li-Ion Full Cells Containing Silicon Alloy

The Effect of Carbon Dioxide on the Cycle Life and Electrolyte Stability of Li-Ion Full Cells Containing Silicon Alloy

Ein Si@SiO_x/C‐Nanokomposit als Anodenmaterial für Lithiumionenbatterien mit hoher Speicherleistung

Effect of Electrolyte Additives on Non-Nano-Si Negative Electrodes Prepared with Polyimide Binder

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Enhancing Electrochemical Performance of Silicon Film Anode by Vinylene Carbonate Electrolyte Additive

Cited by 110 publications

References 18 publications

The Effect of Carbon Dioxide on the Cycle Life and Electrolyte Stability of Li-Ion Full Cells Containing Silicon Alloy

The Effect of Carbon Dioxide on the Cycle Life and Electrolyte Stability of Li-Ion Full Cells Containing Silicon Alloy

Ein Si@SiOx/C‐Nanokomposit als Anodenmaterial für Lithiumionenbatterien mit hoher Speicherleistung

Effect of Electrolyte Additives on Non-Nano-Si Negative Electrodes Prepared with Polyimide Binder

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Product

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Ein Si@SiO_x/C‐Nanokomposit als Anodenmaterial für Lithiumionenbatterien mit hoher Speicherleistung