Crystal-Collapse-Induced Synthesis of High-Capacitance LaCoO _x/Co-Doped Carbon-Based Supercapacitors

Abstract

The development of high-performance, reproducible carbon (C)-based supercapacitors remains a significant challenge because of limited specific capacitance. Herein, we present a novel strategy for fabricating LaCoO _x and cobalt (Co)-doped nanoporous C (LaCoO _x/Co@ZNC) through the carbonization of Co/Zn-zeolitic imidazolate framework (ZIF) crystals derived from a PVP-Co/Zn/La precursor. The unique ZIF structure effectively disrupted the graphitic C framework, preserved the Co active sites, and enhanced the electrical conductivity. The synergistic interaction between pyridinic nitrogen and Co ions further promoted redox reactions. In addition, the formation of a hierarchical pore structure through zinc sublimation facilitated electrolyte diffusion. The resulting LaCoO _x/Co@ZNC exhibited exceptional electrochemical performance, delivering a remarkable specific capacitance of 2,789 F/g at 1 A/g and outstanding cycling stability with 92% capacitance retention after 3,750 cycles. Our findings provide the basis for a promising approach to advancing C-based energy storage technologies.

Keywords

Supercapacitor / High capacitance / Carbon electrode / Doping / Crystal-collapse

References

[1] Shi H. Activated carbons and double layer capacitance. Electrochim Acta, 1996, 41(10): 1633-1639

[2] Qu DY. Studies of the activated carbons used in double-layer supercapacitors. J Power Sour, 2002, 109(2): 403-411

[3] Gamby J, Taberna PL, Simon P, et al. Studies and characterisations of various activated carbons used for carbon/carbon supercapacitors. J Power Sour, 2001, 101(1): 109-116

[4] Chmiola J, Yushin G, Gogotsi Y, et al. Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer. Science, 2006, 313(5794): 1760-1763

[5] Feng G, Qiao R, Huang J, et al. Ion distribution in electrified micropores and its role in the anomalous enhancement of capacitance. ACS Nano, 2010, 4(4): 2382-2390

[6] Kalluri RK, Konatham D, Striolo A, et al. Aqueous NaCl solutions within charged carbon-slit pores: partition coefficients and density distributions from molecular dynamics simulations. J Phys Chem C, 2011, 115(28): 13786-13795

[7] Griffin JM, Forse AC, Tsai WY, et al. In situ NMR and electrochemical quartz crystal microbalance techniques reveal the structure of the electrical double layer in supercapacitors. Nat Mater, 2015, 14(8): 812-819

[8] Zhai ZZ, Zhang LH, Du TM, et al. A review of carbon materials for supercapacitors. Mater Des, 2022, 221: 111017

[9] Wang YM, Wang X, Li XF, et al. A high-performance, tailorable, wearable, and foldable solid-state supercapacitor enabled by arranging pseudocapacitive groups and MXene flakes on textile electrode surface. Adv Funct Mater, 2021, 31(7): 2008185

[10] Abdah M, Azman MAA, Kulandaivalu NHN, et al. Review of the use of transition-metal-oxide and conducting polymer-based fibres for high-performance supercapacitors. Mater Des, 2020, 186: 108199

[11] Kwak MJ, Ramadoss A, Yoon KY, et al. Single-step synthesis of N-doped three-dimensional graphitic foams for high-performance supercapacitors. ACS Sustain Chem Eng, 2017, 5(8): 6950-6957

[12] Zheng S, Xue H, Pang H, et al. Supercapacitors based on metal coordination material. Coord Chem Rev, 2018, 373: 2-21

[13] Liu XX, Shi CD, Zhai CW, et al. Cobalt-based layered metal–organic framework as an ultrahigh capacity supercapacitor electrode material. ACS Appl Mater Interfaces, 2016, 8(7): 4585-4591

[14] Chaikittisilp W, Hu M, Wang H, et al. Nanoporous carbons through direct carbonization of a zeolitic imidazolate framework for supercapacitor electrodes. Chem Commun, 2012, 48(58): 7259-7261

[15] Hu M, Reboul J, Furukawa S, et al. Direct Carbonization of Al-based porous coordination polymer for synthesis of nanoporous carbon. J Am Chem Soc, 2012, 134(6): 2864-2867

[16] Torad NL, Salunkhe RR, Li Y, et al. Electric double-layer capacitors based on highly graphitized nanoporous carbons derived from ZIF-67. Chem Eur J, 2014, 20(26): 7895-7900

[17] Rahma A, Munir MM, Prasetyo A, et al. Intermolecular interactions and the release pattern of electrospun curcumin-polyvinyl(pyrrolidone) fiber. Biol Pharm Bull, 2016, 39(2): 163-173

[18] Díaz E, Valenciano RB, Katime IA. Study of complexes of poly(vinyl pyrrolidone) with copper and cobalt on solid state. J Appl Polym Sci, 2004, 93(4): 1512-1518

[19] Deng J, Dai Z, Hou J, et al. Morphologically tunable MOF nanosheets in mixed matrix membranes for CO₂ separation. Chem Mater, 2020, 32(10): 4174-4184

[20] Han X, Ling X, Wang Y, et al. Generation of nanoparticle, atomic-cluster, and single-atom cobalt catalysts from zeolitic imidazole frameworks by spatial isolation and their use in zinc-air batteries. Angew Chem, 2019, 58(16): 5359-5364

[21] Chen YZ, Wang C, Wu ZY, et al. From bimetallic metal-organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis. Adv Mater, 2015, 27: 5010-5016

[22] Li BQ, Zhao CX, Chen S, et al. Framework-Porphyrin-derived single-atom bifunctional oxygen electrocatalysts and their applications in Zn–air batteries. Adv Mater, 2019, 31(19): 1900592

[23] Li Z, He H, Cao H, et al. Atomic Co/Ni dual sites and Co/Ni alloy nanoparticles in N-doped porous Janus-like carbon frameworks for bifunctional oxygen electrocatalysis. Appl Catal B, 2019, 240: 112-121

[24] Wang F, Xu P, Shi N, et al. Polymer-bubbling for one-step synthesis of three-dimensional cobalt/carbon foams against electromagnetic pollution. J Mater Sci Technol, 2021, 93: 7-16

[25] Han X, Hu M, Yu J, et al. Dual confinement of LaCoO _x modified Co nanoparticles for superior and stable ammonia decomposition. Appl Catal B, 2023, 328: 122534

[26] Wang Y, Li X, Han X, et al. Ternary Mo₂C/Co/C composites with enhanced electromagnetic waves absorption. Chem Eng J, 2020, 387: 124159

[27] Zhou J, Lian J, Hou L, et al. Ultrahigh volumetric capacitance and cyclic stability of fluorine and nitrogen co-doped carbon microspheres. Nat Commun, 2015, 6(1): 8503

[28] Chi ZL, Liu ZY, Liu WB, et al. Inverse opal structured Pt/TiO₂–MnO _y photothermocatalysts for enhanced toluene degradation activity. J Mater Chem A, 2024

[29] Bharti A, Thangavel R, Natarajan R. Promising Co/NC nanocomposite electrode material derived from zeolitic imidazolate framework for high performance and durable aqueous symmetric supercapacitor. J Energy Storage, 2020, 32: 101969

[30] Liu Q, Dongling W, Wang T, Wang C, Jia D. Pre‐Oxidating and pre‐carbonizing to regulate the composition and structure of coal tar pitch: the fabrication of porous carbon for supercapacitor applications. Adv Funct Mater, 2024

[31] Chen B, Wu D, Wang T, et al. Porous carbon generation by burning starch-based intumescent flame retardants for supercapacitors. Chem Eng J, 2024, 486: 150353

[32] Pachfule P, Shinde D, Majumder M, et al. Fabrication of carbon nanorods and graphene nanoribbons from a metal–organic framework. Nat Chem, 2016, 8(7): 718-724

[33] Ferrari AC, Basko DM. Raman spectroscopy as a versatile tool for studying the properties of graphene. Nat Nanotechnol, 2013, 8(4): 235-246

[34] Lu F, Kong W, Su K, et al. Activating the pseudocapacitance of multiple-doped carbon foam via long-term charge-discharge circulation. Chem Eng Sci, 2023, 265: 118232

[35] Thommes M, Kaneko K, Neimark AV, et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution. Pure Appl Chem, 2015, 87(9–10): 1051-1069

[36] Liu C, Wang J, Li J, et al. Electrospun ZIF-based hierarchical carbon fiber as an efficient electrocatalyst for the oxygen reduction reaction. J Mater Chem A, 2017, 5(3): 1211-1220

[37] Chen X, Wang X, Fang D, et al. A review on C1s XPS-spectra for some kinds of carbon materials. Fuller Nanotub Carbon Nanostruct, 2020, 28(12): 1048-1058

[38] Faisal SN, Haque E, Noorbehesht N, et al. Pyridinic and graphitic nitrogen-rich graphene for high-performance supercapacitors and metal-free bifunctional electrocatalysts for ORR and OER. RSC Adv, 2017, 7(29): 17950-17958

[39] Wang D, Chen Y, Wang H, et al. N-doped porous carbon anchoring on carbon nanotubes derived from ZIF-8/polypyrrole nanotubes for superior supercapacitor electrodes. Appl Surf Sci, 2018, 457: 1018-1024

[40] Zhao Y, Liu M, Deng X, et al. Nitrogen-functionalized microporous carbon nanoparticles for high performance supercapacitor electrode. Electrochim Acta, 2015, 153: 448-455

[41] Wang T, Kou Z, Mu S, et al. 2D Dual-metal zeolitic-imidazolate-framework-(ZIF)-derived bifunctional air electrodes with ultrahigh electrochemical properties for rechargeable zinc–air batteries. Adv Funct Mater, 2018, 28(5): 1705048

[42] Sahoo R, Pal A, Pal T, et al. Proportion of composition in a composite does matter for advanced supercapacitor behavior. J Mater Chem A, 2016, 4(44): 17440-17454

[43] Liu WJ, Yuan M, Lian JB, et al. Embedding partial sulfurization of iron–cobalt oxide nanoparticles into carbon nanofibers as an efficient electrode for the advanced asymmetric supercapacitor. Tungsten, 2023, 5(1): 118-129

[44] Yang W, Zhu W, Liu H, et al. Regulating the coordination environment of Co@C catalysts for selective hydrogenation of adiponitrile to hexamethylenediamine. J Catal, 2024, 430: 115312

[45] Lombardo EA, Tanaka K, Toyoshima I. XPS characterization of reduced LaCoO₃ perovskite. J Catal, 1983, 80(2): 340-349

[46] Moorthi K, Sivakumar B, Chokkiah B, et al. Morphological impact of perovskite-structured lanthanum cobalt oxide (LaCoO₃) nanoflakes toward supercapacitor applications. ACS Appl Nano Mater, 2024, 7(16): 18511-18522

[47] Wang Y, Tao S, An Y. Superwetting monolithic carbon with hierarchical structure as supercapacitor materials. Microporous Mesoporous Mater, 2012, 163: 249-258

[48] Devi B, Jain A, Roy B, et al. Cobalt-embedded N-doped carbon nanostructures for oxygen reduction and supercapacitor applications. ACS Appl Nano Mater, 2020, 3(7): 6354-6366

[49] Elumalai P, Vasan H, Munichandraiah N. Electrochemical studies of cobalt hydroxide—an additive for nickel electrodes. J Power Sour, 2001, 93(1): 201-208

[50] Yan J, Ren CE, Maleski K, et al. Flexible MXene/graphene films for ultrafast supercapacitors with outstanding volumetric capacitance. Adv Funct Mater, 2017, 27(30): 1701264

[51] Pech D, Brunet M, Durou H, et al. Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon. Nat Nanotechnol, 2010, 5(9): 651-654

[52] Pu X, Zhao D, Fu C, et al. Understanding and calibration of charge storage mechanism in cyclic voltammetry curves. Angew Chem Int Ed, 2021, 60(39): 21310-21318

[53] Patil DR, Koteswararao B, Begari K, et al. Cobalt cyclotetraphosphate (Co₂P₄O₁₂): a new high-performance electrode material for supercapacitors. ACS Appl Energy Mater, 2019, 2(4): 2972-2981

[54] Xu S, Li Y, Mo T, et al. Highly matched porous MXene anodes and graphene cathodes for high-performance aqueous asymmetric supercapacitors. Energy Storage Mater, 2024, 69: 103379

[55] Li J, J, Xu S, Li Y, , et al. Suppressing the self-discharge of MXene-based supercapacitors by liquid crystal additive. Nano Energy, 2023, 115: 108754

[56] Xu S, Yang H, Li Y, et al. Rolling flexible double-MXenes Ti₃C₂T _x/V₂CT _x hybrid films for microsupercapacitors. Chem Eng J, 2023, 464: 142645

[57] Xu S, Yan S, Chen X, et al. Vertical porous Ti₃CNT _x/rGO hybrid aerogels with enhanced capacitive performance. Chem Eng J, 2023, 459: 141528