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Red Phosphorus Embedded Cross Link Structural Carbon Films as Flexible Anodes for Highly Reversible Li-Ion Storage Jiafeng Ruan, Tao Yuan, Yuepeng Pang, Xinbo Xu, Junhe Yang, Wenbin Hu, Cheng Zhong, Zi-Feng Ma, Xuanxuan Bi, and Shiyou Zheng ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b12556 • Publication Date (Web): 29 Sep 2017 Downloaded from http://pubs.acs.org on September 30, 2017
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ACS Applied Materials & Interfaces
Red Phosphorus Embedded Cross Link Structural Carbon Films as Flexible Anodes for Highly Reversible Li-Ion Storage Jiafeng Ruan,a,‡ Tao Yuan,a,‡ Yuepeng Pang,a Xinbo Xu,a Junhe Yang,a Wenbin Hu,b,c Cheng Zhong,b,c* Zi-Feng Ma,d Xuanxuan Bi,e and Shiyou Zhenga* a
School of Materials Science and Engineering, University of Shanghai for Science
and Technology, Shanghai 200093, China
b
Tianjin Key Laboratory of Composite and Functional Materials, School of Material
Science and Engineering, Tianjin University, Tianjin 300072, China
c
Key Laboratory of Advanced Ceramics and Machining Technology (Ministry of
Education), Tianjin University, Tianjin 300072, China
d
Shanghai Electrochemical Energy Devices Research Center, Department of
Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
e
Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont,
IL, USA
‡ Mr. Jiafeng Ruan and Dr. Tao Yuan contributed equally to this work.
KEYWORDS: Red phosphorus, Binder-free, Flexible, Anode, Li-ion battery
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ABSTRACT: Red phosphorus (P) is considered to be one of the most attractive anodic materials for lithium ion batteries (LIBs) due to its high theoretical capacity of 2596 mAh g-1. However, intrinsic characters such as the poor electronic conductivity and large volume expansion at lithiation impede the development of red P. Here, we design a new strategy to embed red P particles into a cross-link-structural carbon film (P-C film), in order to improve the electronic conductivity and accommodate the volume expansion. The red P/carbon film is synthesized via vapor phase polymerization (VPP) following with pyrolysis process, working as flexible binder-free anode for LIBs. High cycle stability and good rate capability are achieved by the P-C film anode. With 21 % P content in the film, it displays a capacity of 903 mAh g-1 after 640 cycles at a current density of 100 mA g-1, and 460 mAh g-1 after 1000 cycles at 2.0 A g-1. Additionally, the Coulombic efficiency reaches almost to 100 % for each cycle. The superior properties of the P-C films together with their facile fabrication make this material attractive for further flexible and high energy density LIBs applications.
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ACS Applied Materials & Interfaces
1. INTRODUCTION
Rechargeable LIBs have been widely used as green electrical energy storage due to their relatively higher energy and power densities.1-5 Graphite anode was generally used in commercial LIBs, which suffers from limited theoretical capacity (372 mAh g-1) and restricted rate performance.6-8 Therefore, a great deal of efforts have been devoted to explore and develop alternative high capacity anode materials, such as porous amorphous carboneous materials,9-11 Phosphorus- (P-) based composites,12,13 Silicon- (Si-) based composites,14-15 transition metal oxides and nitrides,16-19 etc. Among these high capacity anode materials, P and its composites show great potential for practical applications due to its abundance, environmentally benign and they possess high theoretical specific capacity of 2596 mAh g-1 based on the reaction: 3Li+ + P + 3e- ↔ Li3P.20-22 Phosphorous has three allotropes, white P, black P, and red P.23 White P is toxic and chemically unstable, which is not suitable for the application in LIBs.24 Black P has good thermodynamic stability and conductivity, but the complex preparation process limits its large-scale applications.24-26 Among the three allotropes, red P is more chemically stable than white P, environmentally benign, and abundant, which makes it a promising candidate for the next generation high-energy anodic materials. Although red P has been reported previously in the literature as an active anodic material for LIBs,13,21 it is still plagued by low Coulombic efficiency and poor cycle life, especially at high charge/discharge rates. These obstacles arise mainly from its poor electronic conductivity (
