Few-layer phosphorene: An emerging electrode material for electrochemical energy storage

doi:10.1016/j.apmt.2018.12.008

Applied Materials Today

Volume 15, June 2019, Pages 18-33

https://doi.org/10.1016/j.apmt.2018.12.008 Get rights and content

Highlights

•
The review introduces the phosphorene electrodes for batteries and supercapacitors.
•
Future possibilities and opportunities of phosphorene electrodes are suggested.
•
The key challenges of phosphorene electrodes are provided in this thriving field.

Abstract

The emergence of phosphorene in 2014 augments the family of two-dimensional (2D) materials, which soon triggered tremendous interest in the field of physics, chemistry, biomedicine, and materials science. Considering the tunable band gap, large interlayer spacing (0.53 nm), high charge carrier mobility and strong in-plane anisotropy, tremendous research efforts have been dedicated to the exploration of phosphorene's applications in electrochemical energy storage systems. This review, both theoretically and experimentally, introduces the state-of-the-art development of few-layer phosphorene as the electrode material for electrochemical energy storage systems. The discussed electrochemical energy storage systems involve Li-ion batteries, Na-ion batteries, K-ion batteries, Li-S batteries and supercapacitors. More importantly, perspectives on future possibilities and opportunities of electrochemical energy storage devices based on few-layer phosphorene are also suggested, including dual-ion batteries and metal-ion hybrid capacitors. Finally, the key challenges of phosphorene electrodes are provided for the further research in this thriving field.

Graphical abstract

A comprehensive summary on few-layer phosphorene as electrode materials for electrochemical energy storage systems is provided in this review.

Introduction

Innovative research on functional materials is the foundation of modern technology. Since the discovery of graphene in 2004 and the related Noble Prize in 2010, there is great interest in two-dimensional (2D) materials, which now have been expanding to transition metal dichalcogenide (MoS₂, WS₂, NbSe₂, etc.), layered double hydroxides, transition-metal carbides/nitrides (MXenes), elemental analogs of graphene (borophene, silicene, germanene, etc.), nitrides (BN, GaN, Co₂N, etc.), metal organic frameworks (MOF) and covalent organic frameworks (COF), etc. [1], [2], [3]. In this scientific background, monolayer and few-layer phosphorene nanosheets were exfoliated from bulk black phosphorus (BP) crystals using a scotch-tape-based microcleavage method in 2014 [4], [5], which soon became a research hotspot after graphene. Actually, BP was discovered about 100 years ago [6]. Below 550 °C at atmospheric pressure, BP is the most thermodynamically stable among the other allotrope of phosphorus (such as red, violet and white phosphorus). Importantly, BP has a layered structure consisting of phosphorene sheets stacked by van der Waals dispersion. In few-layer phosphorene, each phosphorus atom covalently connects to three neighboring phosphorus atoms through sp³ hybridized orbitals and forms a puckered honeycomb structure with the zigzag direction along the x-axis and the armchair direction along the y-axis, making the phosphorus atoms arrangement different from that of graphene.

Few-layer phosphorene possesses intrinsically tunable direct bandgaps (from 0.3 eV to 2 eV), high carrier mobility (≈200–1000 cm² V⁻¹ s⁻¹), superior mechanical flexibility, and anisotropic nature in electronic and phonon dispersions. These fascinating properties endow few-layer phosphorene with a wide range of application, such as field-effect transistors [4], photodetectors [7], photovoltaic devices [8], [9], biosensors [10], gas sensors [11], superconductor [12], thermoelectric conversion [13], nano-electromechanical resonators [14], photosensitizer [15], photocatalysts [16] and electrocatalysts [17]. In addition to these important applications, another promising application of few-layer phosphorene is the electrochemical energy storage systems including rechargeable batteries and supercapacitors. Phosphorus can react with three Li or Na atoms to form Li₃P and Na₃P compounds with a high theoretical specific capacity up to 2596 mAh g⁻¹ as an anode for metal-ion battery [18]. For few-layer phosphorene, owing to its high active surface area and much available space for accumulating electrostatic charges, phosphorene is naturally a promising candidate for supercapacitors [19].

In the past three years, there have been many high quality reviews focusing on the progress about the application of BP and phosphorene [20], [21], [22], anisotropic physical properties of BP [23], liquid phase exfoliation of BP [24], fundamental physical properties of phosphorene [25], biomedical applications of BP [26], [27], photonics and electronics device [28], [29]. As exhibited in Fig. 1a, the graph of publications on phosphorene and the associated numbers of citation reflect the increasing research interest in phosphorene and its applications. Moreover, several groups have devoted their pioneering efforts in BP and phosphorene-based electrochemical energy storage devices, as illustrated in the timeline of key developments in the area of phosphorene-based electrode materials (Fig. 1b). Nevertheless, most of the previous reviews paid much attention to the electrochemical performance of BP anode [30], [31], [32], [33], [34], [35], [36], [37], [38]. Moreover, there is a rapid increase in new electrochemical energy storage devices, such as K-ion batteries and micro-supercapacitors, offering strong motivation for an updated review on phosphorene-based electrochemical energy storage systems. Herein, this review, by combining theory and experiment, we provide recent advances in few-layer phosphorene-based electrode materials for electrochemical energy storage applications, involving Li-ion batteries, Na-ion batteries, supercapacitors and state-of-the-art devices (K-ion batteries, micro-supercapacitors). We also highlight its future possible energy storage applications (like Mg-ion batteries, dual-ion batteries and metal ion capacitors) with the aim of providing a new insight for the design and development of new advanced electrochemical energy storage devices based on few-layer phosphorene.

Section snippets

Preparation of few-layer phosphorene

Few-layer phosphorene nanosheets are mainly prepared by top-down exfoliation methods using bulk crystal, such as the well-known scotch tape technique (also known as micromechanical delamination) and liquid phase exfoliation technique with ultrasound (typically 20–50 kHz). Scotch tape exfoliation was the first technique used to produce phosphorene from bulk layered BP solids [4]. However, the scotch tape approach is not scalable and the yield is extremely low. Liquid phase exfoliation is one of

Few-layer phosphorene for rechargeable batteries

Currently, the electrode materials based on few-layer phosphorene have been utilized as anodes or cathode substrates for Li-ion batteries, Na-ion batteries, K-ion batteries and Li-S batteries.

Few-layer phosphorene for supercapacitors

Different from rechargeable batteries, supercapacitors are power devices that can be quickly charged and discharged within several seconds. Moreover, supercapacitors usually possess very excellent cycling lifespan (>10 000 cycles) [92], [93], [94]. Depending upon the storage mechanism, supercapacitors can be divided into two categories: electrochemical double layer capacitors (EDLCs) and pseudocapacitors [95]. For BP and phosphorene electrodes, they usually present typical electrochemical

Perspective on the future applications of few-layer phosphorene in electrochemical energy devices

A lot of new electrochemical energy devices are emerging as promising alternatives for current metal-ion batteries and supercapacitors. In this section, we will succinctly introduce our perspective on the potential applications of few-layer phosphorene in some other electrochemical energy devices even though there are no related experimental reports so far.

Summary and outlook

In summary, few-layer phosphorene have been exploited as promising electrode materials for various electrochemical energy storage devices. In the case of the synthesis of few-layer phosphorene, significant achievements have been made through top-down methods. While bottom-up methods are relatively rare to prepare phosphorene. For the application in the field of Li and Na ion battery, phosphorene-based nanocomposites materials have shown high specific capacities, long cycle lifespans and

Acknowledgements

This work was financially supported by the Key Scientific Research Projects for Higher Education in Henan Province (Grant No. 17A140010), the Excellent Youth Project of Education Department Foundation of Hunan Province of China (16B117) and the National Natural Science Foundation of China (21675050).

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¹: These authors contributed equally to this work.

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Applied Materials Today

ReviewFew-layer phosphorene: An emerging electrode material for electrochemical energy storage

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Preparation of few-layer phosphorene

Few-layer phosphorene for rechargeable batteries

Few-layer phosphorene for supercapacitors

Perspective on the future applications of few-layer phosphorene in electrochemical energy devices

Summary and outlook

Acknowledgements

J. Power Sources

Electrochem. Commun.

Nano Energy

Nano Energy

J. Power Sources

J. Power Sources

Two-dimensional materials from high-throughput computational exfoliation of experimentally known compounds

Nat. Nanotechnol.

Evolutionary selection growth of two-dimensional materials on polycrystalline substrates

Nat. Mater.

Dual-template synthesis of 2D mesoporous polypyrrole nanosheets with controlled pore size

Adv. Mater.

Black phosphorus field-effect transistors

Nat. Nanotechnol.

Phosphorene: an unexplored 2D semiconductor with a high hole mobility

ACS Nano

Two new modifications of phosphorus

J. Am. Chem. Soc.

Waveguide-integrated black phosphorus photodetector with high responsivity and low dark current

Nat. Photonics

Multifunctional homogeneous lateral black phosphorus junction devices

Chem. Mater.

Bilayer phosphorene: effect of stacking order on bandgap and its potential applications in thin-film solar cells

J. Phys. Chem. Lett.

Sensitive detection of carcinoembryonic antigen using stability-limited few-layer black phosphorus as an electron donor and a reservoir

Small

Ultrahigh sensitivity and layer-dependent sensing performance of phosphorene-based gas sensors

Nat. Commun.

Intercalant-independent transition temperature in superconducting black phosphorus

Nat. Commun.

Hinge-like structure induced unusual properties of black phosphorus and new strategies to improve the thermoelectric performance

Sci. Rep.

Black phosphorus nanoelectromechanical resonators vibrating at very high frequencies

Nanoscale

Ultrathin black phosphorus nanosheets for efficient singlet oxygen generation

J. Am. Chem. Soc.

Strain engineering for phosphorene: the potential application as a photocatalyst

J. Phys. Chem. C

Applications of phosphorene and black phosphorus in energy conversion and storage devices

Adv. Energy Mater.

A phosphorene-graphene hybrid material as a high-capacity anode for sodium-ion batteries

Nat. Nanotechnol.

Flexible all-solid-state supercapacitors based on liquid-exfoliated black-phosphorus nanoflakes

Adv. Mater.

Phosphorene: from theory to applications

Nat. Rev. Mater.

Phosphorene: fabrication, properties, and applications

J. Phys. Chem. Lett.

Recent advances in synthesis, properties, and applications of phosphorene

npj 2D Mater. Appl.

Black phosphorus nanosheets: synthesis, characterization and applications

Small

Solution processing of two-dimensional black phosphorus

Chem. Commun.

Electronic structure and the properties of phosphorene and few-layer black phosphorus

J. Phys. Soc. Jpn.

Omnipotent phosphorene: a next-generation, two-dimensional nanoplatform for multidisciplinary biomedical applications

Chem. Soc. Rev.

Few-layered black phosphorus: from fabrication and customization to biomedical applications

Small

Recent advances in black phosphorus-based photonics, electronics, sensors and energy devices

Mater. Horiz.

The rising star of 2D black phosphorus beyond graphene: synthesis, properties and electronic applications

2D Mater.

Recent advances on black phosphorus for energy storage, catalysis, and sensor applications

Adv. Mater.

Advanced phosphorus-based materials for lithium sodium-ion batteries: recent developments and future perspectives

Review
Few-layer phosphorene: An emerging electrode material for electrochemical energy storage