Scalable spray-dried graphite/CNT/silicon composites with enhanced cycling stability for Li-ion battery anodes

Abstract

This study presents a scalable and cost-effective spray-drying method for synthesizing graphite/silicon/carbon nanotube (G-Si-CNT) composites as high-performance anodes for lithium-ion batteries. By integrating graphite fines, nano-silicon (nSi), and a low loading (1 wt%) of single-walled CNTs, the resulting composites exhibit enhanced cycling stability and rate capability. The spray-drying process ensures uniform particle morphology and strong adhesion between components, effectively mitigating the mechanical degradation typically caused by silicon’s volume expansion during cycling. Electrochemical tests reveal that the G-15% nSi-1%CNT composite achieves a capacity retention of 95.3% after 100 cycles with a discharge capacity of 630 mAh·g^-1 (3.15 mAh·cm^-2), outperforming CNT-free counterparts. While CNTs increase solid electrolyte interphase-related losses due to higher surface area, their mechanical and conductive benefits outweigh this drawback. Impedance spectroscopy and post-mortem analyses confirm reduced charge-transfer resistance and improved structural integrity due to CNTs incorporation. The use of low-cost by-products from natural graphite spheroidization and low CNTs content offers significant economic advantages, positioning these composites as promising candidates for scalable, high-energy lithium-ion battery anodes.

Keywords

Li-ion battery / anode / graphite fine / silicon / carbon nanotube / spray-drying

References

[1] Li J.,Fleetwood J.,Hawley W. B.,Kays W.. From materials to cell: state-of-the-art and prospective technologies for lithium-ion battery electrode processing Chem. Rev. 2022 122 903 56

[2] Shen X.,Zhang X.,Ding F..et al. Advanced electrode materials in lithium batteries: retrospect and prospect Energy Mater. Adv. 2021 2021 1205324

[3] Ge M.,Cao C.,Biesold G. M..et al. Recent advances in silicon-based electrodes: from fundamental research toward practical applications Adv. Mater. 2021 33 e2004577

[4] Wang L.,Yu J.,Li S..et al. Recent advances in interface engineering of silicon anodes for enhanced lithium-ion battery performance Energy Storage Mater. 2024 66 103243

[5] Sun L.,Liu Y.,Wang L.,Jin Z.. Advances and future prospects of micro-silicon anodes for high-energy-density lithium-ion batteries: a comprehensive review Adv. Funct. Mater. 2024 34 2403032

[6] Kim N.,Kim Y.,Sung J.,Cho J.. Issues impeding the commercialization of laboratory innovations for energy-dense Si-containing lithium-ion batteries Nat. Energy 2023 8 921 33

[7] Jin B.,Liao L.,Shen X..et al. Advancement in research on silicon/carbon composite anode materials for lithium-ion batteries Metals 2025 15 386

[8] He Z.,Zhang C.,Zhu Z.,Yu Y.,Zheng C.,Wei F.. Advances in carbon nanotubes and carbon coatings as conductive networks in silicon-based anodes Adv. Funct. Mater. 2024 34 2408285

[9] Park B. H.,Jeong J. H.,Lee G.,Kim Y.,Roh K. C.,Kim K.. Highly conductive carbon nanotube micro-spherical network for high-rate silicon anode J. Power Sources 2018 394 94 101

[10] Dressler R. A.,Dahn J. R.. Optimization of Si-containing and SiO based anodes with single-walled carbon nanotubes for high energy density applications J. Electrochem. Soc. 2024 171 030520

[11] Zhang H.,Zhang X.,Jin H..et al. A robust hierarchical 3D Si/CNTs composite with void and carbon shell as Li-ion battery anodes Chem. Eng. J. 2019 360 974 81

[12] Kim K.,Moon D.,Jo M.,Ahn H.. Carbon nanotube-interlocked Si/CNF self-supporting electrode using continuable spraying architecture system for flexible lithium-ion batteries Appl. Surf. Sci. 2024 656 159663

[13] Wang H.,Nie G.,Wang Z..et al. Carbon nanofibers with uniformly embedded silicon nanoparticles as self-standing anode for high-performance lithium-ion battery Colloids Surf. A-Physicochem. Eng. Asp. 2023 671 131653

[14] Hong J.,Zhang J.,Li X.,Guo Y.,Zhou X.,Liu Z.. Graphene-wrapped composites of si nanoparticles, carbon nanofibers, and pyrolytic carbon as anode materials for lithium-ion batteries ACS Appl. Nano Mater. 2023 6 10138 47

[15] Xu J.,Yin Q.,Li X..et al. Spheres of graphene and carbon nanotubes embedding silicon as mechanically resilient anodes for lithium-ion batteries Nano Lett. 2022 22 3054 61

[16] Li Y.,Yan K.,Lee H.,Lu Z.,Liu N.,Cui Y.. Growth of conformal graphene cages on micrometre-sized silicon particles as stable battery anodes Nat. Energy 2016 1 15029

[17] Xu Q.,Sun J.,Li J.,Yin Y.,Guo Y.. Scalable synthesis of spherical Si/C granules with 3D conducting networks as ultrahigh loading anodes in lithium-ion batteries Energy Storage Mater. 2018 12 54 60

[18] Chen H.,Hou X.,Chen F..et al. Milled flake graphite/plasma nano-silicon@carbon composite with void sandwich structure for high performance as lithium ion battery anode at high temperature Carbon 2018 130 433 40

[19] Lee D.,Kondo A.,Lee S..et al. Controlled swelling behavior and stable cycling of silicon/graphite granular composite for high energy density in lithium ion batteries J. Power Sources 2020 457 228021

[20] An W.,Xiang B.,Fu J..et al. Three-dimensional carbon-coating silicon nanoparticles welded on carbon nanotubes composites for high-stability lithium-ion battery anodes Appl. Surf. Sci. 2019 479 896 902

[21] Li P.,Hwang J. Y.,Sun Y. K.. Nano/microstructured silicon-graphite composite anode for high-energy-density Li-ion battery ACS Nano 2019 13 2624 33

[22] Xia H.,Mu X.,Zhou J..et al. Realization of high-capacity coulombic efficiency in sodium alginate/carbon nanotube double network coated Si-anode for lithium-ion batteries Sust. Mater. Tech. 2024 40 e00940

[23] Chae S.,Choi S. H.,Kim N.,Sung J.,Cho J.. Integration of graphite and silicon anodes for the commercialization of high-energy lithium-ion batteries Angew. Chem. Int. Ed. Engl. 2020 59 110 35

[24] Abrego-martinez J. C.,Wang Y.,Vanpeene V.,Roué L.. From waste graphite fines to revalorized anode material for Li-ion batteries Carbon 2023 209 118004

[25] Martínez-Criado G.,Villanova J.,Tucoulou R..et al. ID16B: a hard X-ray nanoprobe beamline at the ESRF for nano-analysis J. Synchrotron Radiat. 2016 23 344 52 PMC5297598

[26] Berg S.,Kutra D.,Kroeger T..et al. ilastik: interactive machine learning for (bio)image analysis Nat. Methods 2019 16 1226 32

[27] Schindelin J.,Arganda-Carreras I.,Frise E..et al. Fiji: an open-source platform for biological-image analysis Nat. Methods 2012 9 676 82 PMC3855844

[28] Tranchot A.,Idrissi H.,Thivel P. X.,Roué L.. Impact of the slurry pH on the expansion/contraction behavior of silicon/carbon/carboxymethylcellulose electrodes for Li-ion batteries J. Electrochem. Soc. 2016 163 A1020 6

[29] Liu X. H.,Zhong L.,Huang S.,Mao S. X.,Zhu T.,Huang J. Y.. Size-dependent fracture of silicon nanoparticles during lithiation ACS Nano 2012 6 1522 31

[30] Raccichini R.,Amores M.,Hinds G.. Critical review of the use of reference electrodes in li-ion batteries: a diagnostic perspective, batteries Batteries 2019 5 12

[31] Zhang W.,Fang L.,Yue M.,Yu Z.. Improved electrochemical performance of modified natural graphite anode for lithium secondary batteries J. Power Sources 2007 174 766 9

[32] Lin Z.,Liu T.,Ai X.,Liang C.. Aligning academia and industry for unified battery performance metrics Nat. Commun. 2018 9 5262 PMC6288112

[33] Müller J.,Michalowski P.,Kwade A.. Impact of silicon content and particle size in lithium-ion battery anodes on particulate properties and electrochemical performance Batteries 2023 9 377

[34] Wu F.,Dong Y.,Su Y..et al. Benchmarking the effect of particle size on silicon anode materials for lithium-ion batteries Small 2023 19 e2301301

[35] Zhang Z.,Sun S.,Zhang W..et al. Internally inflated core-buffer-shell structural Si/EG/C composites as high-performance anodes for lithium-ion batteries Sci. China Mater. 2022 65 2949 57

[36] Shih J.,Chen Y.,James Li Y..et al. Suppressed volume change of a spray-dried 3D spherical-like Si/graphite composite anode for high-rate and long-term lithium-ion batteries ACS Sustainable Chem. Eng. 2022 10 12706 20

[37] Li M.,Hou X.,Sha Y..et al. Facile spray-drying/pyrolysis synthesis of core–shell structure graphite/silicon-porous carbon composite as a superior anode for Li-ion batteries J. Power Sources 2014 248 721 8

[38] Wu H.,Zheng L.,Du N..et al. Constructing densely compacted graphite/Si/SiO₂ ternary composite anodes for high-performance Li-ion batteries ACS Appl. Mater. Interfaces 2021 13 22323 31

[39] Luo H.,Wang Q.,Wang Y..et al. Nano-silicon embedded in MOFs-derived nitrogen-doped carbon/cobalt/carbon nanotubes hybrid composite for enhanced lithium ion storage Appl. Surf. Sci. 2020 529 147134

[40] Hao Y.,Yang X.,Gao Y..et al. High-toughness design of micron-sized silicon/carbon composite as practical anode for lithium-ion batteries Chem. Eng. J. 2025 515 163258

[41] Jin D.,Yang X.,Ou Y..et al. Thermal pyrolysis of Si@ZIF-67 into Si@N-doped CNTs towards highly stable lithium storage Sci. Bull. 2020 65 452 9

[42] Meng K.,Guo H.,Wang Z..et al. Self-assembly of porous-graphite/silicon/carbon composites for lithium-ion batteries Powder Technol. 2014 254 403 6

[43] Pham T. K.,Snook G. A.,Glass D.,Ellis A. V.. Lithium-ion diffusion behaviour in silicon nanoparticle/graphite blended anodes J. Power Sources 2025 638 236623

[44] Olson J. Z.,López C. M.,Dickinson E. J. F.. Differential analysis of galvanostatic cycle data from li-ion batteries: interpretative insights and graphical heuristics Chem. Mater. 2023 35 1487 513

[45] Nguyen Q. A.,Haridas A. K.,Terlier T.,Biswal S. L.. Prelithiation effects in enhancing silicon-based anodes for full-cell lithium-ion batteries using stabilized lithium metal particles ACS Appl. Energy Mater. 2023 6 5567 79

[46] Karkar Z.,Guyomard D.,Roué L.,Lestriez B.. A comparative study of polyacrylic acid (PAA) and carboxymethyl cellulose (CMC) binders for Si-based electrodes Electrochim. Acta 2017 258 453 66

[47] Karkar Z.,Mazouzi D.,Hernandez C. R.,Guyomard D.,Roué L.,Lestriez B.. Threshold-like dependence of silicon-based electrode performance on active mass loading and nature of carbon conductive additive Electrochim. Acta 2016 215 276 88

[48] Cao Z.,Zheng X.,Qu Q.,Huang Y.,Zheng H.. Electrolyte design enabling a high-safety and high-performance Si anode with a tailored electrode-electrolyte interphase Adv. Mater. 2021 33 e2103178

[49] Wang H.,Chao Y.,Li J..et al. What is the real origin of single-walled carbon nanotubes for the performance enhancement of Si-based anodes? J. Am. Chem. Soc. 2024 146 17041 53

[50] Li H.,Yao B.,Li M..et al. Three-dimensional carbon nanotubes buffering interfacial stress of the silicon/carbon anodes for long-cycle lithium storage ACS Appl. Mater. Interfaces 2024 16 53665 74

[51] Kawabe N.,Nakata Y.,Kashiki S..et al. Low-elasticity SW-/MW-CNT hybrid binder for enhanced cycling stability in SiO_x-based lithium-ion battery anodes ACS Appl. Energy Mater. 2025 8 10717 28

[52] Wang Y.,Abrego-martinez J. C.,Barry A. Y.,Quéméré S.,Roué L.. Revalorization of graphite fines via carbon nanotube integration for sustainable fast-charging Li-ion battery anodes J. Power Sources 2025 659 238445

[53] Chae S.,Xu Y.,Yi R..et al. A micrometer-sized silicon/carbon composite anode synthesized by impregnation of petroleum pitch in nanoporous silicon Adv. Mater. 2021 33 e2103095

[54] Zhang D.,Lu J.,Pei C.,Ni S.. Electrochemical activation, sintering, and reconstruction in energy-storage technologies: origin, development, and prospects Adv. Energy Mater. 2022 12 2103689

[55] Hovington P.,Dontigny M.,Guerfi A..et al. In situ scanning electron microscope study and microstructural evolution of nano silicon anode for high energy Li-ion batteries J. Power Sources 2014 248 457 64

[56] Luo L.,Wu J.,Luo J.,Huang J.,Dravid V. P.. Dynamics of electrochemical lithiation/delithiation of graphene-encapsulated silicon nanoparticles studied by in-situ TEM Sci. Rep. 2014 4 3863 PMC3900994