Vinyl ethylene sulfite as a new additive in propylene carbonate-based electrolyte for lithium ion batteries

Yao, Wanhao; Zhang, Zhongru; Gao, Jun; Li, Jie; Xu, Jie; Wang, Zhoucheng; Yang, Yong

doi:10.1039/b905162g

Cited by 118 publications

(95 citation statements)

References 18 publications

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“…The calculated frontier orbital energies of solvents and additives other than ES are consistent with related DFT calculations. 69,70 In the presence of ES, any SEI film formed during charging are considered to be more soluble to solvated Li + (ES) n , than to Li + (PC) n moieties. Additionally, comparison of these findings to voltammetric investigations in experimental work using similar solvents, suggests that while PC does not in itself help to form SEI that prevent co-intercalation and thus graphite exfoliation, ES can potentially initiate reduction processes in PC leading to more effective SEI film formation at the graphite surface.…”

Section: Resultsmentioning

confidence: 99%

The Role of Carbonate and Sulfite Additives in Propylene Carbonate-Based Electrolytes on the Formation of SEI Layers at Graphitic Li-Ion Battery Anodes

Bhatt¹,

O’Dwyer²

2014

J. Electrochem. Soc.

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Density functional theory (DFT) was used to investigate the effect of electrolyte additives such as vinylene carbonate (VC), vinyl ethylene carbonate (VEC), vinyl ethylene sulfite (VES), and ethylene sulfite (ES) in propylene carbonate (PC)-based Li-ion battery electrolytes on SEI formation at graphitic anodes. The higher desolvation energy of PC limits Li + intercalation into graphite compared to solvated Li + in EC. Li + (PC) 3 clusters are found to be unstable with graphite intercalation compounds and become structurally deformed, preventing decomposition mechanisms and associated SEI formation in favor of co-intercalation that leads to exfoliation. DFT calculations demonstrate that the reduction decomposition of PC and electrolyte additives is such that the first electron reduction energies scale as ES > VES > VEC >PC. The second electron reduction follows ES > VES > VEC > VC > PC. The reactivity of the additives under consideration follows ES > VES > VEC > VC. The data demonstrate the supportive role of certain additives, particularly sulfites, in PC-based electrolytes for SEI film formation and stable cycling at graphitic carbon-based Li-ion battery anodes without exfoliation or degradation of the anode structure. The lithium ion battery has been one of the primary power sources driving the digital age, and witnessed a resurgence in interest with the advent of nanoscale materials and advances in cell performance. [1][2][3][4][5][6] Much of the processes and mechanisms underpinning carbonate-based electrolytes in Li-ion batteries, particularly at the anode, still need to be resolved. 7,8 Some commonly used organic solvents are ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) etc. These organic electrolytes are decomposed during intercalation of lithium ions into graphite anode, resulting in the formation of the crucial solid electrolyte interphase (SEI) film. [9][10][11] This film plays an important role in determining capacity retention, cycle life and safety concerns in lithium ion batteries.12,13 SEI films typically comprise Li 2 O, Li 2 CO 3 and related carbonates, LiF (depending on salt used), and polymer phases together with olefins.14 Effective SEI films provide stable surface passivation without significant reduction in electron conduction (higher transfer resistance). On carbon (graphite) anodes, stable SEI films are crucial for stable cycling and are formed below ∼0.8 V vs. Li + /Li. In practical applications of lithium-ion batteries, the selection of the electrode material is critical, particularly when using high surface area nanomaterials. 15 Enhanced chemical stability against electrolyte oxidation and reduction, high ionic conductivity, high boiling points, and low melting points are required, as well as the ability to solvate a wide range of lithium salts such as LiPF 6 , LiBF 4 or LiClO 4 , 16-21 in aprotic and organic solvents such as ethylene carbonate (EC), propylene carbonate (PC), their mixtures, and ...

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Section: Resultsmentioning

confidence: 99%

The Role of Carbonate and Sulfite Additives in Propylene Carbonate-Based Electrolytes on the Formation of SEI Layers at Graphitic Li-Ion Battery Anodes

Bhatt¹,

O’Dwyer²

2014

J. Electrochem. Soc.

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“…In addition, the dQ/dE-E chart shows that the irreversible reduction of the short conjugated carbon bonds mainly occurs in the voltage range from 1.2 to 1.0 V, as indicated by the shaded area in Figure 3b. [26]. Unlike the conventional Li/S batteries, the Li/SPAN cell only shows a slightly sloped voltage plateau in the discharging and charging voltage profile (see Figure 1a).…”

Section: Cycling Characteristics Of Li/span Cellmentioning

confidence: 99%

“…In this case, the SPAN polymer backbones can act as the conducting polymer to provide extra capacities when over-discharged. The redox potential and reversibility of the organic solvents, conducting polymers and carbonaceous materials are varied with the delocalization degree of electrons, i.e., the degree of carbon conjugation, for example, 1.4-1.5 V (irreversible) for single carbon double bonds [25,26], ~1.3 V (reversible) for linear n-doped polyacetylene [32], 1.0-1.2 V (irreversible) for the short conjugated carbon bonds in the SPAN as shown in Figure 3b, and 0.1-0.3 V (highly reversible) for plane graphite [33]. Therefore, it is reasonable to conclude that the extra capacities of the Li/SPAN cell below 1 V are due to the reversible redox of the highly delocalized conjugated carbon bonds in the desulfurized SPAN.…”

Section: Over-discharging and Over-charging Characteristicsmentioning

confidence: 99%

Understanding of Sulfurized Polyacrylonitrile for Superior Performance Lithium/Sulfur Battery

2014

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Sulfurized polyacrylonitrile (SPAN) is one of the most important sulfurized carbon materials that can potentially be coupled with the carbonaceous anode to fabricate a safe and low cost "all carbon" lithium-ion battery. However, its chemical structure and electrochemical properties have been poorly understood. In this discussion, we analyze the previously published data in combination with our own results to propose a more reasonable chemical structure that consists of short -S x -chains covalently bonded onto cyclized, partially dehydrogenated, and ribbon-like polyacrylonitrile backbones. The proposed structure fits all previous structural characterizations and explains many unique electrochemical phenomena that were observed from the Li/SPAN cells but have not been understood clearly.

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“…Up to now, many film-forming additives such as SO 2 [12], Li 2 CO 3 [13][14][15], K 2 CO 3 [16,17], ethylene sulfite [18], propylene sulfite [19], vinyl ethylene sulfite [20], and vinylethylene carbonate [21][22][23][24][25] were successfully used to improve the electrochemical performance and to modify the surface chemistry of graphite or Si anodes for lithium-ion batteries.…”

Section: Introductionmentioning

confidence: 99%

Influence of vinylene carbonate as an additive on the electrochemical performances of graphite electrode in poly(methyl methacrylate) gel polymer electrolytes

et al. 2015

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Thermal initiation polymerization was used and optimized to prepare poly(methyl methacrylate) gel polymer electrolytes (PMMA-GPE). The impact of vinylene carbonate (VC) on the electrochemical performance of mesophase-pitch-based carbon fibers in PMMA-GPE for lithium-ion batteries was investigated using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and charge-discharge test. As expected, adding VC with a proper concentration of 1 vol% into GPE results in better electrolyte conductivity, cycling performance, and reversible capacity. Combining with Scanning electron microscopy, LSV and CV, detailed EIS investigation was used in order to better understand the modified mechanisms of graphite electrode in GPE with VC. The results reveal that the improvement of electrochemical performance is mainly due to the effective inhibition on growth of the internal resistance, which mainly attributed to the solid electrolyte interphase with an electrochemically and structurally stability mainly formed by the reduction and polymerization of VC at higher potential as restraining the side reaction of the reduction and polymerization of matrix in GPE.

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Vinyl ethylene sulfite as a new additive in propylene carbonate-based electrolyte for lithium ion batteries

Cited by 118 publications

References 18 publications

The Role of Carbonate and Sulfite Additives in Propylene Carbonate-Based Electrolytes on the Formation of SEI Layers at Graphitic Li-Ion Battery Anodes

The Role of Carbonate and Sulfite Additives in Propylene Carbonate-Based Electrolytes on the Formation of SEI Layers at Graphitic Li-Ion Battery Anodes

Understanding of Sulfurized Polyacrylonitrile for Superior Performance Lithium/Sulfur Battery

Influence of vinylene carbonate as an additive on the electrochemical performances of graphite electrode in poly(methyl methacrylate) gel polymer electrolytes

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