A novel approach to synthesize micrometer-sized porous silicon as a high performance anode for lithium-ion batteries

Jia, Haiping; Zheng, Jianming; Song, Junhua; Luo, Langli; Yi, Ran; Estevez, Luis; Zhao, Wengao; Patel, Rajankumar L.; Li, Xin; Zhang, Ji‐Guang

doi:10.1016/j.nanoen.2018.05.048

Cited by 200 publications

(125 citation statements)

References 43 publications

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“…[16] The porous Si electrodes were harvested from the Si||NMC333 cells after 100 cycles and prepared for TEM investigation by embedding the active material to the resin (see details in the Experimental Section). Transmission electron microscopy (TEM) test was employed to characterize the cycled anodes in these three electrolytes.…”

Section: Electrode/electrolyte Interfacesmentioning

confidence: 99%

High‐Performance Silicon Anodes Enabled By Nonflammable Localized High‐Concentration Electrolytes

Jia

Zou

Gao

et al. 2019

Advanced Energy Materials

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electric vehicles. [1] LIBs with the conventional carbonaceous anode materials such as graphite have played a dominant role in the current market of customer electronics and electrical transportation. However, low capacity of carbonaceous anode materials (372 mAh g −1 ) also limits the further increase in energy densities of LIBs. [2] In this regard, silicon (Si)-based anode is considered as one of the most promising anode candidates in further boosting the specific energy of LIBs because Si has one of the highest practical capacity of 3579 mAh g −1 among various anode materials and a relatively low lithiation potential of 0.2 V versus Li/Li + . However, fast capacity fade and large swelling of Si anodes related to their large volume expansion (>300%) upon lithiation greatly hindered their deployment in practical applications. [3] There has been significant progress toward understanding and mitigating the capacity fade in Si-based anodes, including exploiting nanostructured Si materials, [4] porous structures, [5] surface coatings, [6] core-shell structures, [7] and novel binders. [8] However, the development of novel electrolytes for Si-based anodes is relatively slow because most researches have been focused on the structure development of Si electrodes. The conventional electrolytes for Si anodes are LiPF 6 /carbonate-based electrolytes with a certain amount of fluoroethylene carbonate (FEC) as an additive or cosolvent (from 5% to 10% by weight in the electrolytes). [9] Linear carbonate solvents usually have relatively low flashpoints, so they are easily ignited and may lead to safety problems under certain extreme conditions. [10] In addition, the formed solid electrolyte interphase (SEI) on anode surface in conventional carbonate electrolytes is unstable and cannot withstand the large volume changes of Si during cycling. Although the introduction of FEC in the conventional LiPF 6 / carbonate electrolytes can improve the cycling performance of Si anodes, increased amount of FEC may lead to increased gassing in full cells. Because such high content of FEC in the electrolytes may form a detrimental cathode electrolyte interface (CEI) on cathode surface and generate a serious gassing issue especially at high charge cutoff voltages and elevated temperatures, which lead to impedance increase, capacity fading and safety issue of the Si-based full cells. Therefore, the Silicon anodes are regarded as one of the most promising alternatives to graphite for high energy-density lithium-ion batteries (LIBs), but their practical applications have been hindered by high volume change, limited cycle life, and safety concerns. In this work, nonflammable localized highconcentration electrolytes (LHCEs) are developed for Si-based anodes. The LHCEs enable the Si anodes with significantly enhanced electrochemical performances comparing to conventional carbonate electrolytes with a high content of fluoroethylene carbonate (FEC). The LHCE with only 1.2 wt% FEC can further improve the long-term cycling stability of Si-base...

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Section: Electrode/electrolyte Interfacesmentioning

confidence: 99%

High‐Performance Silicon Anodes Enabled By Nonflammable Localized High‐Concentration Electrolytes

Jia

Zou

Gao

et al. 2019

Advanced Energy Materials

Self Cite

187

139

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“…[25,26] In addition to the XRD analysis, we further performed Raman spectroscopy analysis. More specifically, the cubic ZnS crystal structure can also be confirmed by the observation of the exposed (220) and (2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20) crystal planes along the zone axis of [001], as indicated by d-spacings of lattice fringes in Figure 1f. The morphology of the ZnSi 2 P 3 powder was further examined using field-emission scanning electron microscopy (FESEM; Figure S1, Supporting Information) and low-magnitude transmission electron microscopy (TEM, Figure 1e).…”

Section: Synthesis and Structural Characterizations Of Znsi 2 Pmentioning

confidence: 69%

“…As shown in Figure 4e, the Coulombic efficiency remains at ≈100% after 500 cycles at a current density of 300 mA g −1 while maintaining ≈80.5% of the initial discharge capacity (at 1955 mAh g −1 ). Notably, the Li-storage performance of the ZnSi 2 P 3 /C nanocomposite is superior to most reported P-and Si-based anodes [2,3,6,8,9,11,19,[32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50] in terms of initial Coulombic efficiency and cycling stability (Figure 4g). Notably, the Li-storage performance of the ZnSi 2 P 3 /C nanocomposite is superior to most reported P-and Si-based anodes [2,3,6,8,9,11,19,[32][33][34][35][36][37][38][39][40][41][42][43]…”

Section: Li-storage Performance Of Znsi 2 P 3 /C Nanocompositementioning

confidence: 85%

“…Among all metal-based anode materials, Si is considered the most attractive candidate due to its abundance in the crust of earth, low cost, high theoretical capacity (4200 mAh g −1 according to Li 4.4 Si), and low working potential. [3][4][5][6][7][8][9][10] Unfortunately, the complicated synthesis processes together with low yield greatly increase the cost of LIBs, although the well-designed nanostructure engineering did show better Li-storage performance in certain aspects (e.g., rate performance) compared to the micro-sized Si anodes. To address these issues, various strategies have been developed, including nanostructure engineering, porous structure tuning, and surface modification with coatings.…”

Section: Introductionmentioning

confidence: 99%

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Zn(Cu)Si₂₊_xP₃ Solid Solution Anodes for High‐Performance Li‐Ion Batteries with Tunable Working Potentials

Zhang

et al. 2019

Adv Funct Materials

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Si-based anodes with a stiff diamond structure usually suffer from sluggish lithiation/delithiation reaction due to low Li-ion and electronic conductivity. Here, a novel ternary compound ZnSi 2 P 3 with a cationdisordered sphalerite structure, prepared by a facile mechanochemical method, is reported, demonstrating faster Li-ion and electron transport and greater tolerance to volume change during cycling than the existing Si-based anodes. A composite electrode consisting of ZnSi 2 P 3 and carbon achieves a high initial Coulombic efficiency (92%) and excellent rate capability (950 mAh g −1 at 10 A g −1 ) while maintaining superior cycling stability (1955 mAh g −1 after 500 cycles at 300 mA g −1 ), surpassing the performance of most Si-and P-based anodes ever reported. The remarkable electrochemical performance is attributed to the sphalerite structure that allows fast ion and electron transport and the reversible Li-storage mechanism involving intercalation and conversion reactions. Moreover, the cation-disordered sphalerite structure is flexible to ionic substitutions, allowing extension to a family of Zn(Cu)Si 2+x P 3 solid solution anodes (x = 0, 2, 5, 10) with large capacity, high initial Coulombic efficiency, and tunable working potentials, representing attractive anode candidates for next-generation, high-performance, and low-cost Li-ion batteries.

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“…[52] Alternatively, porousS i/C composites with continuous networks are another type of promising anode candidates, mainly attributed to the high tap density and structural integrity against severe volumetric changes. [53] In addition, the abundant inner pores can not only accommodate the large mechanical strained induced by the expansion of Si but also provide channels for lithium ion transfer. [54] Normally,t he porous Si is first fabricated through diversem ethodologies such as electrochemical etching, [55] metal-assisted chemicale tching, [56] template-assisted processes, [57] magnesiothermic reduction, [58] and dealloying of Si metal alloys.…”

Section: Porous Structuresmentioning

confidence: 99%

Engineering Carbon Distribution in Silicon‐Based Anodes at Multiple Scales

Zhu

Jiang

Yang

2019

Chemistry A European J

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Thes uccessful commercialization of promising silicon-based anode materials has been hampered by their poor cycling stability caused by the huge volume change. Integration of the carbon matrix with silicon-based (C/Sibased) anode materials has been demonstrated to be a powerful solution to achieve satisfactory electrochemical performance. This minireview aims to outline recent devel-opments on C/Si-based composites, with the emphasis on the importance of carbon distribution at multiple scales. In addition, the forms of the carbon framework (carbon sources and doping of heteroatoms) have been summarized. Particularly,anovel C/Si-based hybrid with carbon distributeda t the atomic scale has been highlighted.

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A novel approach to synthesize micrometer-sized porous silicon as a high performance anode for lithium-ion batteries

Cited by 200 publications

References 43 publications

High‐Performance Silicon Anodes Enabled By Nonflammable Localized High‐Concentration Electrolytes

High‐Performance Silicon Anodes Enabled By Nonflammable Localized High‐Concentration Electrolytes

Zn(Cu)Si₂₊_xP₃ Solid Solution Anodes for High‐Performance Li‐Ion Batteries with Tunable Working Potentials

Engineering Carbon Distribution in Silicon‐Based Anodes at Multiple Scales

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A novel approach to synthesize micrometer-sized porous silicon as a high performance anode for lithium-ion batteries

Cited by 200 publications

References 43 publications

High‐Performance Silicon Anodes Enabled By Nonflammable Localized High‐Concentration Electrolytes

High‐Performance Silicon Anodes Enabled By Nonflammable Localized High‐Concentration Electrolytes

Zn(Cu)Si2+xP3 Solid Solution Anodes for High‐Performance Li‐Ion Batteries with Tunable Working Potentials

Engineering Carbon Distribution in Silicon‐Based Anodes at Multiple Scales

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Resources

About

Zn(Cu)Si₂₊_xP₃ Solid Solution Anodes for High‐Performance Li‐Ion Batteries with Tunable Working Potentials