리튬이차전지용 고용량 음극을 위한 구리@코발트산화물 코어-쉘 수지상 기반 3차원 다공성 박막
Three-dimensional porous films consisting of copper@cobalt oxide coreshell dendrites for high-capacity lithium secondary batteries
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Three dimensional (3D) porous structures consisting of Cu@CoO core-shell-type nano-dendrites were synthesized and tested as the anode materials in lithium secondary batteries. For this purpose, first, the 3D porous films comprising Cu@Co core-shell-type nano-dendrites with various thicknesses were fabricated through the electrochemical co-deposition of Cu and Co. Then the Co shells were selectively anodized to form Co hydroxides, which was finally dehydrated to get Cu@CoO nano-dendrites. The resulting electrodes exhibited very high reversible specific capacity almost 1.4~2.4 times the theoretical capacity of commercial graphite, and excellent capacity retention (~90%@50th cycle) as compared with those of the existing transition metal oxides. From the analysis of the cumulative irreversible capacity and morphology change during charge/discharge cycling, it proved that the excellent capacity retention was attributed to the unique structural feature of our core-shell structure where only the thin CoO shell participates in the lithium storage. In addition, our electrodes showed a superb rate performance (70.5%@10.8 C-rate), most likely due to the open porous structure of 3D films, large surface area thanks to the dendritic structure, and fast electron transport through Cu core network.
Abstract
Three dimensional (3D) porous structures consisting of Cu@CoO core-shell-type nano-dendrites were synthesized and tested as the anode materials in lithium secondary batteries. For this purpose, first, the 3D porous films comprising Cu@Co core-shell-type nano-dendrites with various thicknesses were fabricated through the electrochemical co-deposition of Cu and Co. Then the Co shells were selectively anodized to form Co hydroxides, which was finally dehydrated to get Cu@CoO nano-dendrites. The resulting electrodes exhibited very high reversible specific capacity almost 1.4~2.4 times the theoretical capacity of commercial graphite, and excellent capacity retention (~90%@50th cycle) as compared with those of the existing transition metal oxides. From the analysis of the cumulative irreversible capacity and morphology change during charge/discharge cycling, it proved that the excellent capacity retention was attributed to the unique structural feature of our core-shell structure where only the thin CoO shell participates in the lithium storage. In addition, our electrodes showed a superb rate performance (70.5%@10.8 C-rate), most likely due to the open porous structure of 3D films, large surface area thanks to the dendritic structure, and fast electron transport through Cu core network.
참고문헌 (38)
- T. Zhang, "Nanosized tin anode prepared by laser-induced vapor deposition for lithium ion battery", J. Power Sources, 174, pp.770~773 (2007)
- S. Han, "Simple synthesis of hollow tin dioxide microspheres and their application to lithium-ion battery anodes", Adv. Funct. Mater, 15, pp.1845~1850 (2005)
- K. Peng, "Silicon nanowires for rechargeable lithium-ion battery anodes", Appl. Phy. Lett, 93, pp.033105~ (2008)
- Y. Yao, "Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life", Nano Lett, 11, pp.2949~2954 (2011)
- H. H. Li, "Shale-like Co3O4for high performance lithium", sodium ion batteries, 2016, pp.4, 8242~8248
- D. Yang, "Synthesis of cobalt phosphides and their application as anodes for lithium ion batteries", ACS Appl. Mater. Interfaces, 5, pp.1093~1099 (2013)
- H. Li, "Reduced graphene oxide", boron nitride composite film as a novel binderfree anode for lithium ion batteries with enhanced performances, 2015, pp.166, 197~205
- P. Poizot, "Nano-sized transitionmetal oxides as negative-electrode materials for lithium-ion batteries", Nature, 407, pp.496~499 (2000)
- J. S. Do, "Preparation and characterization of CoO used as anodic material of lithium battery", J. Power Sources, 146, pp.482~486 (2005)
- J. S. Do, "Electrochemical and charge", discharge properties of the synthesized cobalt oxide as anode material in Li-ion batteries, 2006, pp.159, 323~327
- Y. Qin, "CoOCo nanocomposite anode with enhanced electrochemical performance for lithiumion batteries", Electrochim. Acta, 224, pp.90~95 (2017)
- F. D. Wu, "Self-assembled echinus-like nanostructures of mesoporous CoO nanorod@ CNT for lithium-ion batteries", J. Mater. Chem, 21, pp.6636~6641 (2011)
- B. Wan, "Layered mesoporous CoO", reduced graphene oxide with strong interfacial coupling as a high-performance anode for lithium-ion batteries, 2020, pp.843, 156050~
- L. H. Wang, "High electrochemical performance and structural stability of CoO nanosheets", CoO film as self-supported anodes for lithium-ion batteries, 2021, pp.47, 5739~5746
- S. W. Song, "Electrochemical studies of nanoncrystalline Mg2Si thin film electrodes prepared by pulsed laser deposition", J. Electrochem. Soc., 150, pp.A121~ (2002)
- H. C. Shin, "Three-dimensional porous copper-tin alloy electrodes for rechargeable lithium batteries", Adv. Funct. Mater, 15, pp.582~586 (2005)
- X. Huang, "Nickel foam-supported porous NiO", Ag film electrode for lithium-Ion batteries, 2008, pp.155, A438~
- H. J. Wang, "Structural and electrochemical properties of a porous nanostructured SnO2 film electrode for lithium-ion batteries", Electrochem. Commun, 12, pp.194~197 (2010)
- J. Qu, "Selfaligned Cu–Si core–shell nanowire array as a high-performance anode for Li-ion batteries", J. Power Sources, 198, pp.312~317 (2012)
- J. Wang, "Cu–Ge core–shell nanowire arrays as three-dimensional electrodes for highrate capability lithium-ion batteries", J. Mater. Chem, 22, pp.1511~1515 (2012)
- G. Pan, "Fabrication of porous Co", NiO core, Electrochem. Commun, pp.2013, 34[DOI]
- W. S. Choi, "Microporous sponge structure with copper-cobalt oxide hybrid nanobranches", J. Alloys Compd, 692, pp.670~675 (2017)
- J. Liu, "Controllable synthesis of cobalt monoxide nanoparticles and the size-dependent activity for oxygen reduction reaction", ACS Catal, 4, pp.2998~3001 (2014)
- S. Grugeon, "An update on the reactivity of nanoparticles Co-based compounds towards Li", Solid State Sci, 5, pp.895~904 (2003)
- J. Deng, "Solution combustion synthesis of cobalt oxides(Co3O4 and Co3O4", CoO)nanoparticles as supercapacitor electrode materials, 2014, pp.132, 127~135
- L. Li, "Amorphization of cobalt monoxide nanocrystals and related explosive gas sensing applications", Nanotechnology, 26, pp.415501~ (2015)
- L. Wang, "Ferric chlorideGraphite Intercalation Compounds as Anode Materials for Li-ion Batteries", ChemSusChem, 7, pp.87~91 (2014)
- J. Xu, "Recent progress in graphite intercalation compounds for rechargeable metal (Li, Na, K, Al)-ion batteries", Adv. Sci., 4, pp.1700146~ (2017)
- H. C. Choi, "Local Structural Characterization for Electrochemical Insertion-Extraction of Lithium into CoO with X-ray Absorption Spectroscopy", J. Phys. Chem. B, 106, pp.9252~9260 (2002)
- J. S. Do, "Cobalt oxide thin film prepared by an electrochemical route for Li-ion battery", J. Power Sources, 189, pp.204~210 (2009)
- C. Chen, "An understanding of anomalous capacity of nano-sized CoO anode materials for advanced Li-ion battery", Electrochem. Commun, 12, pp.496~498 (2010)
- A. K. Rai, "Onestep synthesis of CoO anode material for rechargeable lithium-ion batteries", Ceram. Int, 39, pp.9325~9330 (2013)
- Q. Li, "Extra storage capacity in transition metal oxide lithium-ion batteries revealed by in situ magnetometry", Nat. Mater, 20, pp.76~83 (2021)
- H. Li, "Operando magnetometry probing the charge storage mechanism of CoO lithium-ion batteries", Adv. Mater, 33, pp.2006629~ (2021)
- P. Poizot, "From the vanadates to 3d-metal oxides negative electrodes", Ionics, 6, pp.321~330 (2000)
- M. Dollé, "Experimental evidence for electrolyte involvement in the reversible reactivity of CoO toward compounds at low potential", Electrochem. Solid-State Lett, 5, pp.A18~ (2001)
- W. S. Choi, "Degradation of Co3O4 anode in rechargeable lithium-ion battery : a semi-empirical approach to the effect of conducting material content", J. Solid State Electrochem, 20, pp.345~352 (2016)
- H. R. Jung, "Nickel–tin foam with nanostructured walls for rechargeable lithium battery", J. Power Sources, 196(11), pp.5122~5127 (2011)