A dimensionally stable and fast-discharging graphite–silicon composite Li-ion battery anode enabled by electrostatically self-assembled multifunctional polymer-blend coating

Li, Fusheng; Wu, Yu-Shiang; Chou, Jackey; Wu, Nae‐Lih

doi:10.1039/c4cc09825k

Cited by 44 publications

(39 citation statements)

References 17 publications

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“…Problematically, the intercalated Si, Li 3.75 Si, swells in volume by about 320% during charging. [15] Zhang et al prepared core-shell structure (Si@C) using silicon nanoparticles (Si-NPs) and emulsion polymerization of acrylonitrile, followed by pyrolysis. [8][9][10][11] Naturally, this is unacceptable for practical and industrial applications.…”

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confidence: 99%

“…Such huge volumetric expansion causes large material stresses, resulting in anode cracking, fracturing, loss of electrical contact (delamination), unstable solid electrolyte interface (SEI) and even catastrophic cell failure. [16] The composite [15] retained A composite anode material synthesized using silicon nanoparticles, micrometer sized graphite particles, and starch-derived amorphous carbon (GCSi) offers scalability and enhanced electrochemical performance when compared to existing graphite anodes. To overcome the capacity limitations of carbon, and the mechanical limitations of silicon, manufacturers have moved into composite materials-with the primary structure consisting of graphitic carbon, with silicon nanoparticles implanted within.…”

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In Situ Mechanistic Elucidation of Superior Si‐C‐Graphite Li‐Ion Battery Anode Formation with Thermal Safety Aspects

Parekh

Sediako

Naseri

et al. 2019

Advanced Energy Materials

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understanding of the material synthesis/ fabrication, interfacial behavior, and thermal-chemical stabilities are vital. [3] With electronic appliances requiring stable voltage delivery, the current LIBs employ graphite or mixtures with soft carbons (carbon black) to achieve stable performance at discharge curves. [4] Since 1991, various forms of ordered and disordered (i.e., soft and hard) carbon have been primarily used as anode materials. [5] With graphitic carbon, a compromise was identified, which delivered a theoretical maximum capacity of 372 mAh g −1 , while maintaining stability and cycling characteristics. This stability comes at a cost of battery capacity, as it takes six carbon atoms to bind a single lithium ion (LiC 6 ) during charging process. [6] By contrast, alternative anode materials such as silicon, can bind about four lithium atoms (SiLi 4.4 ), improving energy densities by an order of magnitude. [7] Silicon anodes have garnered huge attention as they provide over ten times more theoretical capacity (3579 mAh g −1 ) than graphite anode. Problematically, the intercalated Si, Li 3.75 Si, swells in volume by about 320% during charging. Such huge volumetric expansion causes large material stresses, resulting in anode cracking, fracturing, loss of electrical contact (delamination), unstable solid electrolyte interface (SEI) and even catastrophic cell failure. [8][9][10][11] Naturally, this is unacceptable for practical and industrial applications. To overcome the capacity limitations of carbon, and the mechanical limitations of silicon, manufacturers have moved into composite materials-with the primary structure consisting of graphitic carbon, with silicon nanoparticles implanted within. First reported by Yoshio and co-workers in 2002, the C/Si composites did improve capacity, but the silicon nanoparticles were difficult to merge with the carbon bulk. [12,13] After repeated cycling, it was found that the particles separate and capacity drops. [14] Li et al. reported fabrication of graphite-Si composite using polymer blends of poly(diallyl dimethyl-ammonium chloride) and poly(sodium 4-styrenesulfonate) to obtain capacity of 450 mAh g −1 with 95% capacity retention after 200 cycles. [15] Zhang et al. prepared core-shell structure (Si@C) using silicon nanoparticles (Si-NPs) and emulsion polymerization of acrylonitrile, followed by pyrolysis. [16] The composite [15] retained A composite anode material synthesized using silicon nanoparticles, micrometer sized graphite particles, and starch-derived amorphous carbon (GCSi) offers scalability and enhanced electrochemical performance when compared to existing graphite anodes. Mechanistic elucidation of the formation steps of tailored GCSi composite are achieved with environmental transmission electron microscopy (ETEM) and thermal safety aspects of the composite anode are studied for the first time using specially designed multimode calorimetry for coin cell studies. Electrochemical analysis of the composite anode demonstrates a high initial discharge capaci...

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In Situ Mechanistic Elucidation of Superior Si‐C‐Graphite Li‐Ion Battery Anode Formation with Thermal Safety Aspects

Parekh

Sediako

Naseri

et al. 2019

Advanced Energy Materials

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“…Unlike Na(digl) 2 C n , the position of sodium is on the centre of carbon hexagon in graphene sheet. Table 1: Interlayer distance (d int ), average Na/Li−O bond length (d Na-O ), relative volume expansion ratio (r vol ), exfoliation energy (E exf ), and intercalation energy (E int ) of Na(digl)C n and Li(digl) 2 C n (n = 18,20,24,28,32 Table 2: Atomic charge of graphene layer, diglyme molecule (C, H, O), and Na or Li atom in t-GICs Na(digl)C n , Na(digl) 2 C n and Li(digl) 2 Energy and environmental issues become increasingly global, actual and vital to all the nations on the earth. This prompts people to cease from mass consumption of fossil fuels, which are being exhausted and moreover cause greenhouse gas emission, and to create new technologies for utilizing renewable and clean energy sources such as solar and wind power.…”

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Ab initio study of sodium cointercalation with diglyme molecule into graphite

Yu¹,

Ri²,

Choe³

et al. 2017

Electrochimica Acta

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The cointercalation of sodium with the solvent organic molecule into graphite can resolve difficulty of forming the stage-I Na-graphite intercalation compound, which is a predominant anode of Na-ion battery. To clarify the mechanism of such cointercalation, we investigate the atomistic structure, energetics, electrochemical properties, ion and electron conductance, and charge transferring upon de/intercalation of the solvated Na-diglyme ion into graphite with ab initio calculations. It is found that the Na(digl) 2 C n compound has the negatively lowest intercalation energy at n ≈ 21, the solvated Na(digl) 2 ion diffuses fast in the interlayer space, and their electronic conductance can be enhanced compared to graphite. The calculations reveal that the diglyme molecules as well as Na atom donates electrons to the graphene layer, resulting in the formation of ionic bonding between the graphene layer and the moiety of diglyme molecule. This work will contribute to the development of innovative anode materials for alkali-ion battery applications.

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“…Silicon is acknowledged as one of the most promising anode candidates owing to its very high theoretical capacity (ca. 3579 mA h g −1 , in the form of Li 3.75 Si), abundance, and moderate potential . Nevertheless, two critical problems must be solved before it can be applied in practice: Firstly, during Li + insertion/extraction the silicon host undergoes volume changes, which causes pulverization and leads to rapid capacity decay upon cycling.…”

Section: Introductionmentioning

confidence: 99%

“…3579 mA hg À1 ,i nt he form of Li 3.75 Si), abundance,a nd moderate potential. [4][5][6][7] Nevertheless,t wo critical problems must be solved before it can be appliedi np ractice:F irstly, during Li + insertion/extractiont he silicon host undergoes volume changes,w hich causes pulverizationa nd leads to rapid capacity decay upon cycling.S econdly, silicon shows poor electronic conductivity because of its semiconductor nature,and this results in poor rate performance. [8][9][10][11] Pioneering works have demonstrated that the construction of nanostructuredp orous silicons with ac onductive wrapping layer is an effective approach to extend cycle life and upgrade rate performance.…”

Section: Introductionmentioning

confidence: 99%

Scalable and Cost‐Effective Preparation of Hierarchical Porous Silicon with a High Conversion Yield for Superior Lithium‐Ion Storage

et al. 2016

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Although some reported porous silicon‐based anode materials manifest excellent lithium‐ion storage properties, their scalable and economical synthesis remains a large obstacle to their industrial application. This work presents a scalable and efficient preparation of hierarchical porous silicon by using cost‐effective porous SiO2 as raw material through a modified magnesiothermic reduction approach, in which a rotatable furnace was employed and the hydrofluoric acid (HF) etching treatment was avoided. Moreover, the reaction has a high conversion yield (>95 %). Subsequently, a carbon layer with a thickness of 7 nm has been conformally wrapped onto the surface of the porous silicon through a chemical vapor deposition (CVD) process. The obtained porous Si@C composite exhibits a high reversible capacity at 0.3 A g−1, and retained ca. 40 % of its capacity even at 8 A g−1. Moreover, it has an excellent capacity retention over 300 cycles. The strategies disclosed in the present work and the novel porous Si@C composite may have great potential for the next generation of lithium‐ion batteries.

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A dimensionally stable and fast-discharging graphite–silicon composite Li-ion battery anode enabled by electrostatically self-assembled multifunctional polymer-blend coating

Cited by 44 publications

References 17 publications

In Situ Mechanistic Elucidation of Superior Si‐C‐Graphite Li‐Ion Battery Anode Formation with Thermal Safety Aspects

In Situ Mechanistic Elucidation of Superior Si‐C‐Graphite Li‐Ion Battery Anode Formation with Thermal Safety Aspects

Ab initio study of sodium cointercalation with diglyme molecule into graphite

Scalable and Cost‐Effective Preparation of Hierarchical Porous Silicon with a High Conversion Yield for Superior Lithium‐Ion Storage

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