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Title: Scalable shear-exfoliation of high-quality phosphorene nanoflakes with reliable electrochemical cycleability in nano batteries

Abstract

Atomically thin black phosphorus (called phosphorene) holds great promise as an alternative to graphene and other two-dimensional transition-metal dichalcogenides as an anode material for lithium-ion batteries (LIBs). But, bulk black phosphorus (BP) suffers from rapid capacity fading and poor rechargeable performance. This work reports for the first time the use of in situ transmission electron microscopy (TEM) to construct nanoscale phosphorene LIBs. This enables direct visualization of the mechanisms underlying capacity fading in thick multilayer phosphorene through real-time capture of delithiation-induced structural decomposition, which serves to reduce electrical conductivity thus causing irreversibility of the lithiated phases. Furthermore, we demonstrate that few-layer-thick phosphorene successfully circumvents the structural decomposition and holds superior structural restorability, even when subject to multi-cycle lithiation/delithiation processes and concomitant huge volume expansion. This finding provides breakthrough insights into thickness-dependent lithium diffusion kinetics in phosphorene. More importantly, a scalable liquid-phase shear exfoliation route has been developed to produce high-quality ultrathin phosphorene using simple means such as a high-speed shear mixer or even a household kitchen blender with the shear rate threshold of ~1.25 × 10 4 s -1. Our results reported here will pave the way for industrial-scale applications of rechargeable phosphorene LIBs.

Authors:
 [1]; ORCiD logo [2];  [3];  [4];  [5];  [6];  [7];  [7];  [7];  [7];  [7];  [7];  [8];  [3];  [9];  [8]
  1. Southeast Univ., Nanjing (China). SEU-FEI Nano-Pico Center; Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.; Joint Research Inst. of Southeast Univ. and Monash Univ., Suzhou (People's Republic of China). Center for Advanced Materials and Manufacture
  2. Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Physics
  3. Southeast Univ., Nanjing (China). School of Electronic Science and Engineering
  4. Univ. of Cambridge (United Kingdom). Engineering Center for Advanced Photonics and Electronics
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  6. China Univ. of Mining and Technology, Xuzhou (People's Republic of China. Research Center for Internet of Things
  7. Southeast Univ., Nanjing (China). SEU-FEI Nano-Pico Center
  8. Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
  9. Southeast Univ., Nanjing (China). SEU-FEI Nano-Pico Center; Joint Research Inst. of Southeast Univ. and Monash Univ., Suzhou (People's Republic of China). Center for Advanced Materials and Manufacture
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1336141
Report Number(s):
BNL-112615-2016-JA
Journal ID: ISSN 2053-1583; R&D Project: MA015MACA; KC0201010
Grant/Contract Number:
SC00112704; AC02-98CH10886
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
2D Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 2; Journal ID: ISSN 2053-1583
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; black phosphorus; phosphorene; shear exfoliation; in situ transmission electron microscopy; electrochemical lithiation/ delithiation; lithium-ion batteries

Citation Formats

Xu, Feng, Ge, Binghui, Chen, Jing, Nathan, Arokia, Xin, Linhuo L., Ma, Hongyu, Min, Huihua, Zhu, Chongyang, Xia, Weiwei, Li, Zhengrui, Li, Shengli, Yu, Kaihao, Wu, Lijun, Cui, Yiping, Sun, Litao, and Zhu, Yimei. Scalable shear-exfoliation of high-quality phosphorene nanoflakes with reliable electrochemical cycleability in nano batteries. United States: N. p., 2016. Web. doi:10.1088/2053-1583/3/2/025005.
Xu, Feng, Ge, Binghui, Chen, Jing, Nathan, Arokia, Xin, Linhuo L., Ma, Hongyu, Min, Huihua, Zhu, Chongyang, Xia, Weiwei, Li, Zhengrui, Li, Shengli, Yu, Kaihao, Wu, Lijun, Cui, Yiping, Sun, Litao, & Zhu, Yimei. Scalable shear-exfoliation of high-quality phosphorene nanoflakes with reliable electrochemical cycleability in nano batteries. United States. doi:10.1088/2053-1583/3/2/025005.
Xu, Feng, Ge, Binghui, Chen, Jing, Nathan, Arokia, Xin, Linhuo L., Ma, Hongyu, Min, Huihua, Zhu, Chongyang, Xia, Weiwei, Li, Zhengrui, Li, Shengli, Yu, Kaihao, Wu, Lijun, Cui, Yiping, Sun, Litao, and Zhu, Yimei. 2016. "Scalable shear-exfoliation of high-quality phosphorene nanoflakes with reliable electrochemical cycleability in nano batteries". United States. doi:10.1088/2053-1583/3/2/025005. https://www.osti.gov/servlets/purl/1336141.
@article{osti_1336141,
title = {Scalable shear-exfoliation of high-quality phosphorene nanoflakes with reliable electrochemical cycleability in nano batteries},
author = {Xu, Feng and Ge, Binghui and Chen, Jing and Nathan, Arokia and Xin, Linhuo L. and Ma, Hongyu and Min, Huihua and Zhu, Chongyang and Xia, Weiwei and Li, Zhengrui and Li, Shengli and Yu, Kaihao and Wu, Lijun and Cui, Yiping and Sun, Litao and Zhu, Yimei},
abstractNote = {Atomically thin black phosphorus (called phosphorene) holds great promise as an alternative to graphene and other two-dimensional transition-metal dichalcogenides as an anode material for lithium-ion batteries (LIBs). But, bulk black phosphorus (BP) suffers from rapid capacity fading and poor rechargeable performance. This work reports for the first time the use of in situ transmission electron microscopy (TEM) to construct nanoscale phosphorene LIBs. This enables direct visualization of the mechanisms underlying capacity fading in thick multilayer phosphorene through real-time capture of delithiation-induced structural decomposition, which serves to reduce electrical conductivity thus causing irreversibility of the lithiated phases. Furthermore, we demonstrate that few-layer-thick phosphorene successfully circumvents the structural decomposition and holds superior structural restorability, even when subject to multi-cycle lithiation/delithiation processes and concomitant huge volume expansion. This finding provides breakthrough insights into thickness-dependent lithium diffusion kinetics in phosphorene. More importantly, a scalable liquid-phase shear exfoliation route has been developed to produce high-quality ultrathin phosphorene using simple means such as a high-speed shear mixer or even a household kitchen blender with the shear rate threshold of ~1.25 × 104 s-1. Our results reported here will pave the way for industrial-scale applications of rechargeable phosphorene LIBs.},
doi = {10.1088/2053-1583/3/2/025005},
journal = {2D Materials},
number = 2,
volume = 3,
place = {United States},
year = 2016,
month = 3
}

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