Synergistic Integration of FeCo₂S₄ Particles with Holey Graphene Hydrogel for Enhanced Performance Solid-state Supercapacitor

Abstract

In this study, the holey graphene was prepared by microwave-assisted chemical etching. The three-dimensional (3D) holey graphene hydrogel was obtained through hydrothermal self-assembly method, followed by the introduction of FeCo₂S₄ particles. The resulting holey graphene hydrogel, characterized by high specific surface area and abundant pores combined with FeCo₂S₄ with high pseudocapacitance by interfacial interaction, shortened the mass transport path and enhanced the specific capacitance. The findings reveal that the holey graphene hydrogel/FeCo₂S₄ (FeCo₂S₄/HGH) composite exhibits high specific capacitance and impressive rate capability (413.4 F·g⁻¹ at 1 A·g⁻¹, 300.4 F·g⁻¹ at 6 A·g⁻¹). The symmetric supercapacitor operated within a stable potential window of 0.1–1.6 V, achieving specific capacitance of 127.5 F·g⁻¹ at 1 A·g⁻¹, and can deliver 37.1 Wh·kg⁻¹ at a power density of 1 499 W·kg⁻¹. Besides, under the current density of 3 A·g⁻¹, the supercapacitor retained 90.8% of its capacitance after 5 000 cycles, demonstrating exceptional cycle stability. This study presents an efficient method for fabricating advanced integrated supercapacitors electrodes with enhanced energy density.

Keywords

holey graphene / FeCo₂S₄/HGH / microwave assisted chemical etching / symmetric supercapacitor

References

[1] ChoiY, ParkM, KimS, et al.. A Stretchable, Fully Self-Healable, Temperature-Tolerant, and Water-Proof Supercapacitor Using TUEG3 Capped Gold Nanosheets on Oxime-Carbamate Bonded Polyurethane Film and Organohydrogel[J]. Chemical Engineering Journal, 2024, 488150 931

[2] LiuF, FanZX. Defect Engineering of Two-Dimensional Materials for Advanced Energy Conversion and Storage[J]. Chemical Society Reviews, 2023, 52(5): 1 723-1 772

[3] DingL, JiangR, TangZL, et al.. Mxene: Nano Engineering and Application as Electrode Materials for Supercapacitors[J]. Journal of Inorganic Materials, 2023, 38(6): 619-633

[4] MalyshevaL. Electronic Structure of Conjugated Oligomers that Are Building Blocks for Achiral and Chiral Graphene Nanoribbons[J]. Chemical Physics Letters, 2024, 836141 048

[5] DaiCY, HeP, LuoLX, et al.. Research Progress of Two-Dimensional Magnetic Materials[J]. Science China Materials, 2023, 66(3): 859-876

[6] PintoMMR, SánchezAAC, CostaDSM, et al.. Agarose Fibers with Glycerol and Graphene Oxide and Functional Properties for Potential Application in Biomaterials[J]. International Journal of Biological Macromolecules, 2023, 253127 204

[7] BanDK, BandaruPR. Graphene and Two-dimensional Materials for Biomolecule Sensing[J]. Annual Review of Biophysics, 2023, 52(1): 487-507

[8] YingYR, LinZZ, HuangHT. Edge/Basal Plane Half-Reaction Separation” Mechanism of Two-Dimensional Materials for Photocatalytic Water Splitting[J]. ACS Energy Letters, 2023, 8(3): 1 416-1 423

[9] TianSJ, PanQQ, LiHW, et al.. Two-Dimensional Material Membrane Fabrication: Progress and Challenges[J]. Current Opinion in Chemical Engineering, 2023, 39100 900

[10] DeP, HalderJ, PriyaS, et al.. Two-Dimensional V₂O₅ Nanosheets as An Advanced Cathode Material for Realizing Low-Cost Aqueous Aluminum-Ion Batteries[J]. ACS Applied Energy Materials, 2023, 6(2): 753-762

[11] LengXY, ChenSY, YangK, et al.. Introduction to Two-Dimensional Materials[J]. Surface Review and Letters, 2020, 28082 140 005

[12] DongSA, GaoWH, ShiKM, et al.. Dielectric-Electrolyte Supercapacitors[J]. Cell Reports Physical Science, 2023, 42101 284

[13] AhmadF, ShahzadA, DanishM, et al.. Recent Developments in Transition Metal Oxide-Based Electrode Composites for Supercapacitor Applications[J]. Journal of Energy Storage, 2024, 81110 430

[14] LuMSupercapacitors: Materials Systems, and Applications, 2013[M]

[15] RasuliH, RasuliR. Nanoparticle-Decorated Graphene/Graphene Oxide: Synthesis, Properties and Applications[J]. Journal of Materials Science, 2023, 58(7): 2 971-2 992

[16] Méndez-ReséndizA, Méndez-RomeroUA, Mendoza-JiménezRA, et al.. Highly Crystalline Selectively Oxidized Graphene for Supercapacitors[J]. FlatChem, 2023, 38100 483

[17] ZhaoX, HaynerCM, KungMC, et al.. Flexible Holey Graphene Paper Electrodes with Enhanced Rate Capability for Energy Storage Applications[J]. ACS Nano, 2011, 5(11): 8 739-8 749

[18] LiaoZW, MaYY, YaoS, et al.. Honeycomb-Patterned Porous Graphene Film for Electrochemical Detection of Dopamine[J]. Applied Surface Science, 2022, 605154 725

[19] MorenghiA, ScaravonatiS, MagnaniG, et al.. Asymmetric Supercapacitors Based on Nickel Decorated Graphene and Porous Graphene Electrodes[J]. Electrochimica Acta, 2022, 424140 626

[20] LiuT, ZhangLY, ChengB, et al.. Holey Graphene for Electrochemical Energy Storage[J]. Cell Reports Physical Science, 2020, 110100 215

[21] ZhengX, JiangJL, BiTT, et al.. FeCo₂S₄@Ni@Graphene Nanocomposites with Rich Defects Induced by Heterointerface Engineering for High-Performance Supercapacitors[J]. ACS Applied Energy Materials, 2021, 4(4): 3 288-3 296

[22] MohamedSG, ChenCJ, ChenCK, et al.. High-Performance Lithium-Ion Battery and Symmetric Supercapacitors Based on FeCo₂O₄ Nanoflakes Electrodes[J]. ACS Applied Materials & Interfaces, 2014, 6(24): 22 701-22 708

[23] YanSX, LuoSH, FengJ, et al.. Rational Design of Flower-Like Fe-Co₂S₄/Reduced Graphene Oxide Films: Novel Binder-Free Electrodes with Ultra-High Conductivity Flexible Substrate for High-Performance All-Solid-State Pseudocapacitor[J]. Chemical Engineering Journal, 2020, 381122 695

[24] MuzykaR, KwokaM, SmędowskiL, et al.. Oxidation Of Graphite by Different Modified Hummers Methods[J]. New Carbon Materials, 2017, 32(1): 15-20

[25] TirunehSN, KangBK, KwagSH, et al.. Synergistically Active NiCo₂S₄ Nanoparticles Coupled with Holey Defect Graphene Hydrogel for High-Performance Solid-State Supercapacitors[J]. Chemistry-A European Journal, 2018, 24(13): 3 263-3 270

[26] YangBB, ZhangW, ZhengWT. Unlocking The Full Energy Densities of Carbon-Based Supercapacitors[J]. Materials Research Letters, 2023, 11(7): 517-546

[27] DuXX, WangWJ, HanM, et al.. Fabrication of Nitrogen/Boron Highly Co-Doped Graphene Electrode for Enhanced Electrochemical Performance[J]. Chemistry Select, 2022, 737e202202645

[28] TangSC, ZhuBG, ShiXL, et al.. General Controlled Sulfidation Toward Achieving Novel Nanosheet-Built Porous Square-FeCo₂S₄-Tube Arrays for High-Performance Asymmetric All-Solid-State Pseudocapacitors[J]. Advanced Energy Materials, 2017, 761 601 985

[29] GuoBS, BandaruS, DaiCL, et al.. Self-Supported FeCo₂S₄ Nanotube Arrays as Binder-Free Cathodes for Lithium-Sulfur Batteries[J]. ACS Applied Materials & Interfaces, 2018, 10(50): 43 707-43 715

[30] SuCY, XuYP, ZhangWJ, et al.. Electrical and Spectroscopic Characterizations of Ultra-Large Reduced Graphene Oxide Monolayers[J]. Chemistry of Materials, 2009, 21(23): 5 674-5 680

[31] TharasanP, SomprasongM, KenyotaN, et al.. Preparation and Electrochemical Performance of Nanostructured Co₃O₄ Particles[J]. Journal of Nanoparticle Research, 2022, 246126

[32] HuangYP, CuiF, HuaMQ, et al.. Hierarchical FeCo₂S₄ Nanotube Arrays Deposited on 3D Carbon Foam as Binder-Free Electrodes for High-Performance Asymmetric Pseudocapacitors[J]. Chemistry-An Asian Journal, 2018, 13(21): 3 212-3 221

[33] AvvaruV S, VincentM, FernandezI J, et al.. Unusual Pseudocapacitive Lithium-ion Storage on Defective Co₃O₄ Nanosheets[J]. Nanotechnology, 2022, 3322225 403

[34] ParkJB, XiongW, GaoY, et al.. Fast Growth of Graphene Patterns by Laser Direct Writing[J]. Applied Physics Letters, 2011, 9812123 109

[35] LiuSH, XuGH, LiJ, et al.. Iron-Cobalt Bi-Metallic Sulfide Nanowires on Ni foam for Applications in High-Performance Supercapacitors[J]. Chem. Electro. Chem., 2018, 5(16): 2 250-2 255

[36] XiW, ZhangYF, ZhangJP, et al.. Constructing MXene Hydrogels and Aerogels for Rechargeable Supercapacitors and Batteries[J]. Journal of Materials Chemistry C, 2023, 11(7): 2 414-2 429

[37] LiuSD, KangL, HuJS, et al.. Realizing Superior Redox Kinetics Of Hollow Bimetallic Sulfide Nanoarchitectures by Defect-Induced Manipulation toward Flexible Solid-State Supercapacitors[J]. Small, 2022, 1852 104 507

[38] SunMX, RenXH, GanZW, et al.. Nanostructured Binary Transition-Metal-Sulfides and Nanocomposites as High-Performance Electrodes for Hybrid Supercapacitors[J]. Applied Physics Reviews, 2024, 112021 318

[39] GanZW, RenXH, LiuMD, et al.. Advances in Design of Copper-Based Nanostructures and Nanocomposites for High-Performance Supercapacitors[J]. Journal of Energy Storage, 2024, 99113 383

[40] XieJL, YangPP, WangY, et al.. Puzzles and Confusions in Supercapacitor and Battery: Theory and Solutions[J]. Journal of Power Sources, 2018, 401: 213-223

[41] RenX, LiMG, QiuLY, et al.. Cationic Vacancies and Interface Engineering on Crystalline-Amorphous Gamma-Phase Ni-Co Oxyhydroxides Achieve Ultrahigh Mass/Areal/Volumetric Energy Density Flexible All-Solid-State Asymmetric Supercapacitor[J]. Journal of Materials Chemistry A, 2023, 11(11): 5 754-5 765

[42] WangJ, XuC, ZhangD, et al.. Porous Polymer Cement Composites for Quasi-Solid Graphene Supercapacitors[J]. Journal of Energy Storage, 2023, 63106 991

[43] MaDD, LvML, ShenY, et al.. Fabrication of Porous Mesh-Like FeCo₂S₄ Nanosheet Arrays on Ni Foam for High Performance All Solid-State Supercapacitors and Water Splitting[J]. Chemistry Select, 2019, 4(6): 1879-1889

[44] ChenHC, JiangJJ, ZhaoYD, et al.. One-Pot Synthesis of Porous Nickel Cobalt Sulphides: Tuning The Composition for Superior Pseudocapacitance[J]. Journal of Materials Chemistry A, 2015, 3(1): 428-437

[45] LiuSD, JunSC. Hierarchical Manganese Cobalt Sulfide Core-Shell Nanostructures for High-Performance Asymmetric Supercapacitors[J]. Journal of Power Sources, 2017, 342: 629-637

[46] LinGY, JiangYL, HeCG, et al.. In Situ Encapsulation of Co₃O₄ Polyhedra in Graphene Sheets for High-Capacitance Supercapacitors[J]. Dalton Transactions, 2019, 48(17): 5 773-5 778

[47] LiBX, TianZ, LiHJ, et al.. Self-Supporting Graphene Aerogel Electrode Intensified by NiCo₂S₄ Nanoparticles for Asymmetric Supercapacitor[J]. Electrochimica Acta, 2019, 314: 32-39

[48] ElsaidMAM, HassanAA, MohamedSG, et al.. Synthesis and Electrochemical Performance of Porous FeCo₂S₄ Nanorods as an Electrode Material for Supercapacitor[J]. Journal of Energy Storage, 2021, 44103 330

[49] AhamedAJ, KanagambalP. Design and Fabrication of Reduced Graphene Oxide (RGO) Incorporated NiCo₂S₄ Hybrid Composites as Electrode Materials for High Performance Supercapacitors[J]. Chemical Physics Impact, 2024, 9100 675

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