Architecture of Necklace-Like Carbon Nanotubes@Silicon Oxycarbide Nanostructure for Stable Lithium Storage

Abstract

Silicon oxycarbide (SiOC) has emerged as a promising candidate for anode materials in lithium-ion batteries (LIBs) due to its unique properties. However, the low electrical conductivity of SiOC limits its practical applications. Herein, a novel necklace-like nanostructure was fabricated through the sol-gel method by embedding SiOC nanospheres in carbon nanotubes (CNTs) to form a stable electronic pathway within the structure. Controlling the hexadecyl trimethyl ammonium bromide (CTAB) content through CTAB removal and centrifugation to separate SiOC and CNTs @ phenylene-bridged mesoporous organosilica (CNTs @ PBMO) before the calcination is important to achieve the necklace-like CNTs @ SiOC nanostructure. The fabricated porous necklace-like CNTs@SiOC nanostructure not only improved the electrical conductivity but also ensured full utilization of SiOC active sites during discharging/ charging along with accelerating ion penetration. As a result, it provided a remarkably long cycling life of up to 1 400 cycles, retaining a specific capacity of 178 mA · h/ g.

Keywords

necklace-like structure / CNTs @ SiOC / sol-gel method / long cycle / lithium-ion battery (LIB)

References

[1] DIOUF B , PODE R . Potential of lithium—ion batteries in renewable energy[J]. Renewable Energy, 2015, 76: 375—380.

[2] TOKI G F I , HOSSAIN M K , REHMAN W U , et al. Recent progress and challenges in silicon— based anode materials for lithium—ion batteries[J]. Industrial Chemistry & Materials, 2024, 2 (2): 226—269.

[3] JIANG M M , CHEN J L , LUO H X , et al. Building interconnected structures with silicon— based nanospheres and TiN ionic fence enables ultrahigh electrochemical stability[J]. Advanced Functional Materials, 2024, 34 (27): 2316568.

[4] SEOK E , CHOI M , PARK D , et al. Synthesis of size—controlled SiOC ceramic materials by silicone oil—based emulsion method for anodes in lithium—ion batteries[J]. Journal of Alloys and Compounds, 2023, 969:172386.

[5] RAHMAN M A , SONG G S , BHATT A I , et al. Nanostructured silicon anodes for high— performance lithium—ion batteries[J]. Advanced Functional Materials, 2016, 26 (5): 647—678.

[6] KU M , PARK D , KIM M , et al. Hydrophobic dispersion—derived Si / rGO nanocomposites in SiOC ceramic matrix as anode materials for high performance lithium—ion batteries[J]. Journal of Materials Chemistry A, 2023, 11 (28): 15277—15285.

[7] WU P F , GUO X X , SU Z M , et al. Preparation of silicon oxycarbide (SiOC) anodes for high performance Li—ion batteries using competitive relationship between crosslinking and polymerization[J]. Chemical Engineering Journal, 2022, 446:137354.

[8] SUJITH R , GANGADHAR J , GREENOUGH M , et al. A review of silicon oxycarbide ceramics as next generation anode materials for lithium—ion batteries and other electrochemical applications[J]. Journal of Materials Chemistry A, 2023, 11 (38): 20324—20348.

[9] HAN Q , ZHANG J Z , CHEN H X , et al. The effect of graphitization degree of carbon and Si—O—C network on the electrochemical performance of SiOC anodes[J]. International Journal of Applied Ceramic Technology, 2024, 21 (3): 2332—2341.

[10] BIN MUJIB S , RASHEED M , SINGH G . Evaluating use of boron— and hafnium—modified polysilazanes for ceramic matrix minicomposites[J]. ACS Omega, 2022, 7 (49): 45325—45335.

[11] MA M B , WANG H J , XIONG L , et al. Self— assembled homogeneous SiOC@C/ graphene with three—dimensional lamellar structure enabling improved capacity and rate performances for lithium ion storage[J]. Carbon, 2022, 186: 273—281.

[12] PRADEEP V S , AYANA D G , GRACZYK— ZAJAC M , et al. High rate capability of SiOC ceramic aerogels with tailored porosity as anode materials for Li—ion batteries[J]. Electrochimica Acta, 2015, 157: 41—45.

[13] FAN S Z , ZHANG J J , CUI S Q , et al. Large— scale synthesis of SiOC composites for stable Li— ion battery anode and dendrite—free Li metal deposition[J]. Chemical Engineering Journal, 2024, 479: 147785.

[14] LEE S H , PARK C , DO K , et al. Maximizing the utilization of active sites through the formation of native nanovoids of silicon oxycarbide as anode materials in lithium—ion batteries[J]. Energy Storage Materials, 2021, 35: 130—141.

[15] ZHU G J , GUO R , LUO W , et al. Boron doping—induced interconnected assembly approach for mesoporous silicon oxycarbide structure[J]. National Science Review, 2021, 8 (6): nwaa152.

[16] PARK J , KIM M , CHOI M , et al. Sb/ C composite embedded in SiOC buffer matrix via dispersion property control for novel anode material in sodium—ion batteries[J]. Journal of Power Sources, 2023, 568:232908.

[17] LI K Z , YUAN G Q , LIU X F , et al. On the practical applicability of rambutan—like SiOC anode with enhanced reaction kinetics for lithium— ion storage[J]. Advanced Functional Materials, 2023, 33 (43):2302348.

[18] XIA K D , LIU X , LIU H , et al. Carbon— enriched SiOC ceramics with hierarchical porous structure as anodes for lithium storage[J]. Electrochimica Acta, 2021, 372:137899.

[19] FENG X M , CHEN H X , ZHANG J Z , et al. Constructing a conductive nest to improve the electrochemical properties of SiOC anodes through CNT additives[J]. Journal of Electronic Materials, 2024, 53 (2): 1074—1082.

[20] BHANDAVAT R , SINGH G . Stable and efficient Li—ion battery anodes prepared from polymer—derived silicon oxycarbide—carbon nanotube shell / core composites[J]. The Journal of Physical Chemistry C, 2013, 117: 11899—1190.

[21] WU Z , CHENG X Q , TIAN D , et al. SiOC nanolayers directly—embedded in graphite as stable anode for high—rate lithium ion batteries[J]. Chemical Engineering Journal, 2019, 375:121997.

[22] LIU W M , JIANG M M , ZHANG F Z , et al. Confined self—assembly of SiOC nanospheres in graphene film to achieve cycle stability of lithium ion batteries[J]. New Journal of Chemistry, 2022, 46 (14): 6519—6527.

[23] SHAO G F , HANAOR D A H , WANG J , et al. Polymer—derived SiOC integrated with a graphene aerogel as a highly stable Li—ion battery anode[J]. ACS Applied Materials & Interfaces, 2020, 12 (41): 46045—46056.

[24] ZHANG Y Y , YANG W , LIU X , et al. Necklace—structured silicon suboxide—based anode materials with multiple carbon networks for stable lithium storage[J]. Advanced Functional Materials, 2024, 34 (25): 2315680.

[25] YANG H , NEAL L , FLORES E E , et al. Role and impact of surfactants in carbon nanotube dispersions and sorting[J]. Journal of Surfactants and Detergents, 2023, 26 (5): 607—622.

[26] RICHARD C , BALAVOINE F , SCHULTZ P , et al. Supramolecular self—assembly of lipid derivatives on carbon nanotubes[J]. Science, 2003, 300 (5620): 775—778.

[27] HUANG Y B , YUAN P , WU Z W , et al. Preparation of surface—silylated and benzene— bridged Ti—containing mesoporous silica for cyclohexene epoxidation[J]. Journal of Porous Materials, 2016, 23 (4): 895—903.

[28] ISLAM M F , ROJAS E , BERGEY D M , et al. High weight fraction surfactant solubilization of single—wall carbon nanotubes in water[J]. Nano Letters, 2003, 3 (2): 269—273.

[29] MANNE S , CLEVELAND J P , GAUB H E , et al. Direct visualization of surfactant hemimicelles by force microscopy of the electrical double layer[J]. Langmuir, 1994, 10 (12): 4409—4413.

[30] BAO Y , WANG T , KANG Q L , et al. Micelle— template synthesis of hollow silica spheres for improving water vapor permeability of waterborne polyurethane membrane[J]. Scientific Reports, 2017, 7: 46638.

[31] ZHANG M , WU Y P , FENG X Z , et al. Fabrication of mesoporous silica—coated CNTs and application in size—selective protein separation[J]. Journal of Materials Chemistry, 2010, 20 (28): 5835—5842.

[32] PENG Y Q , WANG K S , YU M H , et al. An optimized process for in situ formation of multi— walled carbon nanotubes in templated pores of polymer—derived silicon oxycarbide[J]. Ceramics International, 2017, 43 (4): 3854—3860.

[33] HALIM M , HUDAYA C , KIM A Y , et al. Phenyl—rich silicone oil as a precursor for SiOC anode materials for long—cycle and high—rate lithium ion batteries[J]. Journal of Materials Chemistry A, 2016, 4 (7): 2651—2656.

[34] LU K , LI J K . Fundamental understanding of water vapor effect on SiOC evolution during pyrolysis[J]. Journal of the European Ceramic Society, 2016, 36 (3): 411—422.

[35] ERMAKOVA M A , ERMAKOV D Y , PLYASOVA L M , et al. XRD studies of evolution of catalytic nickel nanoparticles during synthesis of filamentous carbon from methane[J]. Catalysis Letters, 1999, 62 (2): 93—97.

[36] SORARÙ G D , D ’ ANDREA G , GLISENTI A . XPS characterization of gel—derived silicon oxycarbide glasses[J]. Materials Letters, 1996, 27 (1/ 2): 1—5.

[37] VASHISTH A , KHATRI S , HAHN S H , et al. Mechanical size effects of amorphous polymer— derived ceramics at the nanoscale: experiments and ReaxFF simulations[J]. Nanoscale, 2019, 11 (15): 7447—7456.

[38] SHI H M , YUAN A B , XU J Q . Tailored synthesis of monodispersed nano/ submicron porous silicon oxycarbide (SiOC) spheres with improved Li—storage performance as an anode material for Li—ion batteries[J]. Journal of Power Sources, 2017, 364: 288—298.

[39] FUKUI H , OHSUKA H , HINO T , et al. A Si—O—C composite anode: high capability and proposed mechanism of lithium storage associated with microstructural characteristics[J]. ACS Applied Materials & Interfaces, 2010, 2 (4): 998—1008.

[40] ZHU G J , JIANG M M , MA Y Y , et al. A carbon network strategy to synthesize silicon— carbon anodes toward regulated morphologies during molten salt reduction[J]. CrystEngComm, 2020, 22 (29): 4894—4902.

[41] DAVID L , BHANDAVAT R , BARRERA U , et al. Silicon oxycarbide glass—graphene composite paper electrode for long—cycle lithium— ion batteries[J]. Nature Communications, 2016, 7:10998.

[42] LIU X , ZHENG M C , XIE K . Mechanism of lithium storage in Si—O—C composite anodes[J]. Journal of Power Sources, 2011, 196 (24): 10667—10672.

Funding

National Natural Science Foundation of China(92163121)

National Natural Science Foundation of China(52122312)