Document Type

Dissertation

Degree

Doctor of Philosophy (PhD)

Major/Program

Materials Science and Engineering

First Advisor's Name

Chunlei Wang

First Advisor's Committee Title

Committee chair

Second Advisor's Name

Norman D. H. Munroe

Second Advisor's Committee Title

Committee member

Third Advisor's Name

Bilal El-Zahab

Third Advisor's Committee Title

Committee member

Fourth Advisor's Name

Wenzhi Li

Fourth Advisor's Committee Title

Committee member

Fifth Advisor's Name

Nezih Pala

Fifth Advisor's Committee Title

Committee member

Keywords

Phosphorus, Energy Storage, Phosphorene, Bipolar Electrochemistry, Electrostatic Spray Deposition, Battery, Supercapacitor

Date of Defense

3-17-2021

Abstract

With the rapid development of modern society, the huge demand for energy storage systems from fossil fuels leads to dramatic increasing of greenhouse gases. Therefore, an efficient green energy storage system with high energy density and stable cyclability is urgently required for advanced electronics. The electrochemical performance of energy storage devices strongly depends on the electrode materials. Among the recent advances on electrode materials, phosphorus as an earth-abundant element with high theoretical specific capacity (2596 mAhg-1) and low cost has attracted intensive attention. From different allotropes of phosphorus, red phosphorus (RP) and black phosphorus (BP) show promising electrochemical behavior in advanced electronic devices such as rechargeable batteries and supercapacitors. However, low conductivity and high volume expansion of phosphorus-based electrodes hindered its real performance in energy storage applications. Moreover, exfoliation of BP into phosphorene nanosheets is still time-consuming, toxic, and leads to high defect concentration. This dissertation is tailored to overcome both materials engineering and eco-friendly and scalable manufacturing issues to make high-performance phosphorus-based electrode materials.

In the first part of this dissertation, RP with sulfurized polyacrylonitrile (RP-SPAN) hybrids were synthesized via electrostatic spray deposition (ESD) and characterized as an anode material for lithium-ion batteries (LIBs). The developed hybrid anode delivered excellent specific capacity up to 1605 mAhg-1 at 0.1 A g-1 at 100 cycles with good cyclability and rate capability. The fabricated electrode improved the conductivity of RP and also endured its large volume changes upon cycling. Moreover, the fabricated RP-based LIBs were evaluated in both frequency and time domains in terms of stationarity, stability, and linearity, as well as degradation with extended charge/discharge cycling. The proposed analysis revealed that the cell is highly nonlinear and time-variant at the low-frequencies spectrum which is in line with the 0.21% average capacity loss per cycle that we computed from consecutive charge/discharge measurements.

Exfoliation and deposition of BP into 2D phosphorene nanosheets through the novel one-step, facile, and environmentally friendly method of bipolar electrochemical exfoliation (BPE) on the feeding electrodes was other major goal of the dissertation. The presence of point defects, grain boundaries, and amorphization of bipolar exfoliated phosphorene nanosheets was evaluated through high-resolution transmission electron microscopy (HRTEM) analysis and density functional theory (DFT) calculations. The HRTEM results revealed that the atomic network of phosphorene nanosheets remains coherent with minor perturbations in the bond lengths. Our DFT results also confirmed the breakage of P-P bonds of phosphorene upon surface oxidation, which results in amorphization. The electrochemical performance of the bipolar exfoliated phosphorene nanosheets with an orthorhombic crystal structure was also evaluated in a symmetric two-electrode configuration for supercapacitor applications. The fabricated device delivered a high power density of 351 mW cm-2 at a constant current load discharge of 500 mA cm-2 with high stability and reversibility for at least 40000 cycles, which is comparable with other 2D material-based devices. The results in this dissertation could open up new horizons to improve the performance of P-based electrodes for energy storage applications. The perspective of this dissertation in the study of P-based electrodes would pave the way for the exploration of novel synthesis techniques and make advancement in the area of energy storage devices.

Identifier

FIDC009570

ORCID

https://orcid.org/0000-0002-0774-8973

Previously Published In

1-Amin Rabiei Baboukani, Iman Khakpour, Vadym Drozd, Chunlei Wang, Liquid-Based Exfoliation of Black Phosphorus into Phosphorene and its Application for Energy Storage Devices, Small Structures, 306, 2000148, 2021.

2-Amin Rabiei Baboukani, Iman Khakpour, Ebenezer Adelowo, Vadym Drozd, Wei Shang, and Chunlei Wang, High-Performance Red Phosphorus-sulfurized polyacrylonitrile Composite by Electrostatic Spray Deposition for Lithium-Ion Batteries, Electrochimica Acta, 345, 136227, 2020.

3-Amin Rabiei Baboukani, Iman Khakpour, Vadym Drozd, Anis Allagui, Chunlei Wang, Single-Step Exfoliation of Black Phosphorus and Deposition of Phosphorene via Bipolar Electrochemistry for Capacitive Energy Storage Application, Journal of Materials Chemistry A, 7(44), 25548-25556, 2019.

Sup video 1 - Exfoliation of BP (BPE).mp4 (1610 kB)
Supporting video for Chapter 6

Available for download on Thursday, August 18, 2022

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