F-doped Carbon Coated Nano-Si Anode with High Capacity: Preparation by Gaseous Fluorination and Performance for Lithium Storage

doi:10.15541/jim20230009

Abstract

Abstract:

Si anodes hold immense potential in developing high-energy Li-ion batteries. But fast failure due to huge volume change upon Li uptake impedes their application. This work reports a facile yet low-toxic gas fluorination way for yielding F-doped carbon-coated nano-Si anode materials. Coating of nano-Si with F-doped carbon containing high defects can effectively protect Si from huge volume change upon Li storage while facilitating Li⁺ transport and formation of stable LiF-rich solid electrolyte interphase (SEI). This anode exhibits high capacities of 1540-580 mAh·g^-1 at various current rates of 0.2-5.0 A·g^-1, while retaining >75% capacity after 200 cycles. This method also addresses the issues of high cost and toxicity of traditional fluorination techniques that use fluorine sources such as XeF₂ and F₂.

Key words: Li-ion battery, Si anode, F-doped carbon, gaseous fluorination method

CLC Number:

TQ152

SU Nan, QIU Jieshan, WANG Zhiyu. F-doped Carbon Coated Nano-Si Anode with High Capacity: Preparation by Gaseous Fluorination and Performance for Lithium Storage[J]. Journal of Inorganic Materials, 2023, 38(8): 947-953.

Figures/Tables 9

Fig. 1 Schematic illustration of the production of Si@C-F

Fig. 2 (a) XRD patterns, (b) Raman spectra, (c) XPS survey scan, (d) high-resolution F1s and (e) Si2p XPS spectra of Si@C and Si@C-F, (f) TGA curve of Si@C-F

Fig. 3 (a-c) SEM images, (d-f) TEM images and (g-i) elemental mapping of Si@C-F

Fig. 4 (a, b) CV curves at a scan rate of 0.1 mV·s-1 and charge-discharge voltage curves at (c, d) 0.2 and (e, f) 0.4 A·g-1 for (a, c, e) Si@C and (b, d, f) Si@C-F anodes

Fig. 5 (a) Cycling stability at a current density of 0.4 A·g-1 with anodes activated by 4 cycles at 0.2 A·g-1 before cycling, and (b) rate capability at various current densities ranging from 0.2 to 5.0 A·g−1 and (c) capacity retention at a current density of 0.2 A·g-1 for lithium storage in Si@C and Si@C-F anode Colorful figures are available on website

Table 1 Comparison of Si@C-F anode with reported Si-based anode in electrochemical performance

Materials	Initial CE	Initial capacity/(mAh·g^-1)	Capacity retention	Ref.
Si@C-F	65.9%	2640	85% (100 cycles) 75 % (cycles)	This work
nano-Si/TiN@ carbon	71%	2716	59.4% (110 cycles)	[20]
Si@C@RGO	74.5%	1474	48.9% (40 cycles)	[21]
Si@FA	65%	1334	68.7% (100 cycles)	[22]
p-Si@C	58%	3460	57.5% (100 cycles)	[23]
Si@void@C	-	900	70% (100 cycles)	[24]
Si/C@C	-	1120	80% (100 cycles)	[25]

Fig. 6 Cycling stability of Si@C-F anodes with different F ratios at a current density of 0.4 A·g-1 with anodes activated by 4-10 cycles at 0.2 A·g-1 before cycling Colorful figures are available on website

Fig. 7 Nyquist plots of the Si@C and Si@C-F anodes (a) before and (b) after cycling at a current density of 0.4 A·g-1

Fig. 8 Top SEM images of (a) Si@C and (d) Si@C-F anodes after cycling; Cross-section SEM images of (b, c) Si@C and (e, f) Si@C-F anodes (b, e) before and (c, f) after cycling; High-resolution (g) F1s and (h) Li1s XPS spectra of SEI on Si@C and Si@C-F anodes after cycling

References 26

[1]	NIU S S, WANG Z Y, YU M L, et al. MXene-based electrode with enhanced pseudocapacitance and volumetric capacity for power- type and ultra-long life lithium storage. ACS Nano, 2018, 12(4): 3928. DOI URL
[2]	SU X, WU Q L, LI J C, et al. Silicon-based nanomaterials for lithium-ion batteries: a review. Advanced Energy Materials, 2014, 4(1): 1300882.
[3]	GE M Z, CAO C Y, GILL M B, et al. Recent advances in silicon- based electrodes: from fundamental research toward practical applications. Advanced Materials, 2021, 33(16): 2004577.
[4]	LI P, ZHAO G Q, ZHENG X B, et al. Recent progress on silicon- based anode materials for practical lithium-ion battery applications. Energy Storage Materials, 2018, 15: 422. DOI URL
[5]	LIU X H, ZHONG L, HUANG S, et al. Size-dependent fracture of silicon nanoparticles during lithiation. ACS Nano, 2012, 6(2): 1522. DOI URL
[6]	LUO W, WANG Y X, CHOU S L, et al. Critical thickness of phenolic resin-based carbon interfacial layer for improving long cycling stability of silicon nanoparticle anodes. Nano Energy, 2016, 27: 255. DOI URL
[7]	DOU F, SHI L Y, CHEN G R, Silicon/carbon composite anode materials for lithium-ion batteries. Electrochemical Energy Reviews, 2019, 2(1): 149. DOI
[8]	JIA H P, ZOU L F, GAO P Y, et al. High-performance silicon anodes enabled by nonflammable localized high-concentration electrolytes. Advanced Energy Materials, 2019, 9(31): 1900784.
[9]	CHOI S H, KWON T W, COSKUN A, et al. Highly elastic binders integrating polyrotaxanes for silicon microparticle anodes in lithium ion batteries. Science, 2017, 357: 279. DOI URL
[10]	LI Z H, ZHANG Y P, LIU T F, et al. Silicon anode with high initial Coulombic efficiency by modulated trifunctional binder for high‐areal-capacity lithium-ion batteries. Advanced Energy Materials, 2020, 10(20): 1903110.
[11]	XU Z L, CAO K, ABOUALI S, et al. Study of lithiation mechanisms of high performance carbon-coated Si anodes by in-situ microscopy. Energy Storage Materials, 2016, 3: 45. DOI URL
[12]	TEKI R, MONI K D, RAHUL K, et al. Nanostructured silicon anodes for lithium ion rechargeable batteries. Small, 2009, 5(20): 2236. DOI URL
[13]	XIA S X, ZHANG X, LUO L L, et al. Highly stable and ultrahigh- rate Li metal anode enabled by fluorinated carbon fibers. Small, 2021, 17: 2006002.
[14]	ZHANG S L, WANG X, HO K S, et al. Raman spectra in a broad frequency region of p-type porous silicon. Journal of Applied Physics, 1994, 76(5): 3016. DOI URL
[15]	HUANG W, WANG Y, LUO G H, et al. 99.9% Purity multi-walled carbon nanotubes by vacuum high-temperature annealing. Carbon, 2003, 41(13): 2585. DOI URL
[16]	MCDOWELL M T, LEE S W, NIX W D, et al. 25th Anniversary article: understanding the lithiation of silicon and other alloying anodes for lithium-ion batteries. Advanced Materials, 2013, 25(36): 4966. DOI URL
[17]	KEY B, MORCRETTE M, TARASCON J M. Pair distribution function analysis and solid state NMR studies of silicon electrodes for lithium ion batteries: understanding the (de)lithiation mechanisms. Journal of American Chemical Society, 2011, 133(3): 503. DOI URL
[18]	GAO H, XIAO L S, PLUMEL I, et al. Parasitic reactions in nanosized silicon anodes for lithium-ion batteries. Nano Letters, 2017, 17(3): 1512. DOI URL
[19]	CHEN J, FAN X L, LI Q, et al. Electrolyte design for LiF-rich solid-electrolyte interfaces to enable high-performance microsized alloy anodes for batteries. Nature Energy, 2020, 5(5): 386. DOI
[20]	ZHANG P, GAO Y Q, RU Q, et al. Scalable preparation of porous nano-silicon/TiN@carbon anode for lithiumion batteries. Applied Surface Science, 2019, 498: 143829.
[21]	SU M R, WAN H F, LIU Y J, et al. Multi-layered carbon coated Si-based composite as anode for lithium-ion batteries. Powder Technology, 2018, 323: 294. DOI URL
[22]	PU J B, QIN J, WANG Y Z, et al. Synthesis of micro-nano sphere structure silicon-carbon composite as anode material for lithium- ion batteries. Chemical Physics Letters, 2022, 806: 140006.
[23]	GAO R S, TANG J, YU X L, et al. A sandwich-like silicon-carbon composite prepared by surface-polymerization for rapid lithium-ion storage. Nano Energy, 2020, 70: 104444.
[24]	GONG X H, ZHENG Y B, ZHENG J, et al. Yolk-shell silicon/ carbon composites prepared from aluminum-silicon alloy as anode materials for lithium-ion batteries. Ionics, 2021, 27: 1939. DOI
[25]	LIA Y R, WANG R Y, ZHANG J W, et al. Sandwich structure of carbon-coated silicon/carbon nanofiber anodes for lithium-ion batteries. Ceramics International, 2019, 45: 16195. DOI URL
[26]	YANG X M AND ROGACH A L. Electrochemical techniques in battery research: a tutorial for nonelectrochemists. Advanced Energy Materials, 2019, 9(25): 1900747.