Three-Dimensional Graphene-Decorated Copper-Phosphide (Cu3P@3DG) Heterostructure as an Effective Electrode for a Supercapacitor

Abstract

Transition metal phosphides already emerged with great interest due to their energy storage capacitance, superior metalloid characteristics, and decent electrical conductivity. To achieve a commercially viable outcome, these electrodes are fabricated with interconnected carbonaceous materials. Herein, we have synthesized hexagonal copper phosphide (Cu 3 P) platelets using chemical vapor deposition (CVD) and integrated it with highly conducting three-dimensional graphene (3DG), leading to a nanohybrid (Cu 3 P@3DG) as a coulombic efficient supercapacitor. This nanohybrid has exhibited a specific capacitance (C sp) of 1,095.85 F/g at 10 mV/s scan rate along with a cycling stability of 95% capacitive retention after 3,000 cycles at a current density of 8.97 A/g. The C sp is almost four times higher and the stability is 1.2 times higher compared to the bare Cu 3 P platelets. We have fabricated an asymmetric supercapacitor (ASC) using Cu 3 P@3DG on graphite as cathode and activated carbon (AC) on graphite as anode (Cu 3 P@3DG//AC) that has shown high specific capacity (108.78 F/g), energy density (8.23 Wh/kg), and power density (439.6 W/kg). Moreover, this ASC has exhibited an excellent life cycle (5,500 consecutive charge-discharge with 96% coulombic efficiency). Therefore, the proposed all-solid-state hybrid device can be considered as a route for next-generation high-performing energy storage devices.

Colloidal Synthesis of Tunable Copper Phosphide Nanocrystals

“…39,40 The tolerance of the Cu 3−x P phase to cation migration without major structural reorganization has been exploited in its demonstration as a candidate anode material for lithium ion batteries 41,42 and in its use as a template in cation exchange to InP nanocrystals. 34,43 In recent years, the nanoscaling of Cu 3−x P has enabled its use in applications including catalysis, 44,45 supercapacitors, 46 detection, 47 and chemodynamic therapy 48 and as a precursor to ternary copper chalcophosphate materials used in photovoltaics. 49,50 The synthesis of low-polydispersity, colloidally stable, and size-tunable Cu 3−x P nanocrystals would enable plasmonic studies with minimal contribution from extrinsic effects.…”

“…According to recent theoretical calculations, the nonstoichiometry of the structure arises from copper vacancies within a phase-homogeneity range of 0.17 < x < 0.33 . The ability of the Cu 3– x P structure to host a wide composition range has been experimentally validated by elemental analysis , and solid-state 31 P nuclear magnetic resonance (NMR) spectroscopy. , The tolerance of the Cu 3– x P phase to cation migration without major structural reorganization has been exploited in its demonstration as a candidate anode material for lithium ion batteries , and in its use as a template in cation exchange to InP nanocrystals. , In recent years, the nanoscaling of Cu 3– x P has enabled its use in applications including catalysis, , supercapacitors, photodetection, and chemodynamic therapy and as a precursor to ternary copper chalcophosphate materials used in photovoltaics. , …”

Metal-Rich Porous Copper Cobalt Phosphide Nanoplates as a High-Rate and Stable Battery-Type Cathode Material for Battery–Supercapacitor Hybrid Devices

“…The GCD tests reveal that the Cu−Co− P//PC BSH device possesses an energy density of 41.3 W h kg −1 at 705 W kg −1 and still retains a reasonable value of 12.1 W h kg −1 at 17.625 kW kg −1 . The energy density of the Cu− Co−P//PC BSH device is higher contrasting with the previously reported BSH devices, including Ni 2 P NS/NF// AC (26 W h kg −1 at 337 W kg −1 ),19 NiCoP/CNF//NiCoP/ CNF (36 W h kg −1 at 1200 W kg −1 ),24 Cu-Co-O-NS//HCP-CNF (21.5 W h kg −1 at 400 W kg −1 ),67 Co 2 P//AC (24 W h kg −1 at 300 W kg −1 ),68 CuCo 2 S 4 /CNT//AC (23.2 W h kg −1 at 402.7 W kg −1 ),69 and Cu 3 P/3DG//AC (8.23 W h kg −1 at 274 W kg −1 ) 70. A cycling measurement was performed at 3 A g −1 to determine cycle performance of the Cu−Co−P//PC BSH device.…”

In-Situ Growth of Urchin Manganese Sulfide Anchored Three-Dimensional Graphene (γ-MnS@3DG) on Carbon Cloth as a Flexible Asymmetric Supercapacitor

“…This not only allows for a great amount of the electrolyte to be accessible for faster mass transfer but also promotes high mechanical flexibility. During rigorous cycling performance, the electroactive materials commonly suffer pulverization. , To mitigate this issue, the general practice is to decorate active material with a porous carbonaceous matrix (such as three-dimensional-graphene; 3DG) for better electrochemical performance. − The carbonaceous materials not only provide high conductive channels for electron movement but also simultaneously minimize unwanted accumulation of metal sulfide. − Out of the three distinct phases of MnS (α, β, and γ), the metastable γ-MnS is a layered hexagonal wurtzite structure that can promote facile intercalation of ions and thereby balance the increased valencies of Mn without hindering its structural deformation that provides a shorter diffusion length …”