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Title: Insights into the Na + Storage Mechanism of Phosphorus-Functionalized Hard Carbon as Ultrahigh Capacity Anodes

Abstract

Hard carbon as a typical anode material for sodium ion batteries has received much attention in terms of its low cost and renewability. Herein, phosphorus-functionalized hard carbon with a specific honeycomb briquette shaped morphology is synthesized via electrospinning technology. When applied as an anode material for Na + storage, it exhibits an impressively high reversible capacity of 393.4 mA h g -1 with the capacity retention up to 98.2% after 100 cycles. According to first-principle calculation, the ultrahigh capacity of the as-prepared anode is ascribed to the enhancement of Na-absorption through formation of P=O and P-C bonds in graphitic layers when doped with phosphorus. Furthermore, the increase of electron density around the Fermi level is found to be mainly caused by O atoms instead of P atoms.

Authors:
 [1];  [2];  [1];  [1];  [1];  [1];  [3];  [2];  [3]; ORCiD logo [2]
  1. Beijing Institute of Technology, Beijing (People's Republic of China)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Beijing Institute of Technology, Beijing (People's Republic of China); Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing (People's Republic of China)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Basic Research Program of China
OSTI Identifier:
1466401
Alternate Identifier(s):
OSTI ID: 1423911
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 8; Journal Issue: 18; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; first-principle calculations; hard carbon; phosphorous-functionalization; sodium ion batteries; ultrahigh capacity

Citation Formats

Li, Yu, Yuan, Yifei, Bai, Ying, Liu, Yuanchang, Wang, Zhaohua, Li, Limin, Wu, Feng, Amine, Khalil, Wu, Chuan, and Lu, Jun. Insights into the Na+ Storage Mechanism of Phosphorus-Functionalized Hard Carbon as Ultrahigh Capacity Anodes. United States: N. p., 2018. Web. doi:10.1002/aenm.201702781.
Li, Yu, Yuan, Yifei, Bai, Ying, Liu, Yuanchang, Wang, Zhaohua, Li, Limin, Wu, Feng, Amine, Khalil, Wu, Chuan, & Lu, Jun. Insights into the Na+ Storage Mechanism of Phosphorus-Functionalized Hard Carbon as Ultrahigh Capacity Anodes. United States. doi:10.1002/aenm.201702781.
Li, Yu, Yuan, Yifei, Bai, Ying, Liu, Yuanchang, Wang, Zhaohua, Li, Limin, Wu, Feng, Amine, Khalil, Wu, Chuan, and Lu, Jun. Tue . "Insights into the Na+ Storage Mechanism of Phosphorus-Functionalized Hard Carbon as Ultrahigh Capacity Anodes". United States. doi:10.1002/aenm.201702781. https://www.osti.gov/servlets/purl/1466401.
@article{osti_1466401,
title = {Insights into the Na+ Storage Mechanism of Phosphorus-Functionalized Hard Carbon as Ultrahigh Capacity Anodes},
author = {Li, Yu and Yuan, Yifei and Bai, Ying and Liu, Yuanchang and Wang, Zhaohua and Li, Limin and Wu, Feng and Amine, Khalil and Wu, Chuan and Lu, Jun},
abstractNote = {Hard carbon as a typical anode material for sodium ion batteries has received much attention in terms of its low cost and renewability. Herein, phosphorus-functionalized hard carbon with a specific honeycomb briquette shaped morphology is synthesized via electrospinning technology. When applied as an anode material for Na+ storage, it exhibits an impressively high reversible capacity of 393.4 mA h g-1 with the capacity retention up to 98.2% after 100 cycles. According to first-principle calculation, the ultrahigh capacity of the as-prepared anode is ascribed to the enhancement of Na-absorption through formation of P=O and P-C bonds in graphitic layers when doped with phosphorus. Furthermore, the increase of electron density around the Fermi level is found to be mainly caused by O atoms instead of P atoms.},
doi = {10.1002/aenm.201702781},
journal = {Advanced Energy Materials},
number = 18,
volume = 8,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 35 works
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Figures / Tables:

Figure 1 Figure 1: a) Schematic diagram of the synthesis of hard carbon anodes by electrospinning method, b) SEM images of HC-P15 precursor, c) magnified SEM image of sample HC-P15, d-e) EDX elemental distribution mapping of sample HC-P15 basde on c). HRTEM images of f) sample HC and g) sample HC-P15, themore » insets show the SAED pictures of corresponding samples.« less

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Works referenced in this record:

Thermal behaviour of lignocellulosic material in the presence of phosphoric acid. Influence of the acid content in the initial solution
journal, September 2006


Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

Better Cycling Performances of Bulk Sb in Na-Ion Batteries Compared to Li-Ion Systems: An Unexpected Electrochemical Mechanism
journal, December 2012

  • Darwiche, Ali; Marino, Cyril; Sougrati, Moulay T.
  • Journal of the American Chemical Society, Vol. 134, Issue 51
  • DOI: 10.1021/ja310347x

Use of Graphite as a Highly Reversible Electrode with Superior Cycle Life for Sodium-Ion Batteries by Making Use of Co-Intercalation Phenomena
journal, July 2014

  • Jache, Birte; Adelhelm, Philipp
  • Angewandte Chemie International Edition, Vol. 53, Issue 38
  • DOI: 10.1002/anie.201403734

Predicting capacity of hard carbon anodes in sodium-ion batteries using porosity measurements
journal, September 2014


Enhanced Sodium Ion Storage Behavior of P2-Type Na 2/3 Fe 1/2 Mn 1/2 O 2 Synthesized via a Chelating Agent Assisted Route
journal, January 2016

  • Bai, Ying; Zhao, Lixiang; Wu, Chuan
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 4
  • DOI: 10.1021/acsami.5b11848

High Capacity Anode Materials for Rechargeable Sodium-Ion Batteries
journal, January 2000

  • Stevens, D. A.; Dahn, J. R.
  • Journal of The Electrochemical Society, Vol. 147, Issue 4
  • DOI: 10.1149/1.1393348

Correlation Between Microstructure and Na Storage Behavior in Hard Carbon
journal, November 2015

  • Zhang, Biao; Ghimbeu, Camélia Matei; Laberty, Christel
  • Advanced Energy Materials, Vol. 6, Issue 1
  • DOI: 10.1002/aenm.201501588

Sodium Storage Behavior in Natural Graphite using Ether-based Electrolyte Systems
journal, November 2014

  • Kim, Haegyeom; Hong, Jihyun; Park, Young-Uk
  • Advanced Functional Materials, Vol. 25, Issue 4
  • DOI: 10.1002/adfm.201402984

Low-Surface-Area Hard Carbon Anode for Na-Ion Batteries via Graphene Oxide as a Dehydration Agent
journal, January 2015

  • Luo, Wei; Bommier, Clement; Jian, Zelang
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 4
  • DOI: 10.1021/am507679x

Sulfur-Doped Carbon with Enlarged Interlayer Distance as a High-Performance Anode Material for Sodium-Ion Batteries
journal, August 2015


Synthesis of Phosphorus-Doped Graphene and its Multifunctional Applications for Oxygen Reduction Reaction and Lithium Ion Batteries
journal, July 2013


Effects of H3PO4 and KOH in carbonization of lignocellulosic material
journal, November 2008

  • Jibril, Baba; Houache, Omar; Al-Maamari, Rashid
  • Journal of Analytical and Applied Pyrolysis, Vol. 83, Issue 2
  • DOI: 10.1016/j.jaap.2008.07.003

Engineering Hierarchical Hollow Nickel Sulfide Spheres for High-Performance Sodium Storage
journal, September 2016

  • Zhang, Dan; Sun, Wenping; Zhang, Yu
  • Advanced Functional Materials, Vol. 26, Issue 41
  • DOI: 10.1002/adfm.201602933

Nitrogen doped porous carbon fibres as anode materials for sodium ion batteries with excellent rate performance
journal, January 2014


Influence of micropore structure on Li-storage capacity in hard carbon spherules
journal, March 2005


A phosphorene–graphene hybrid material as a high-capacity anode for sodium-ion batteries
journal, September 2015


High Power-High Energy Sodium Battery Based on Threefold Interpenetrating Network
journal, January 2016

  • Zhu, Changbao; Kopold, Peter; van Aken, Peter A.
  • Advanced Materials, Vol. 28, Issue 12
  • DOI: 10.1002/adma.201505943

Hard carbon nanoparticles as high-capacity, high-stability anodic materials for Na-ion batteries
journal, January 2016


Nitrogen-Doped Porous Carbon Nanofiber Webs as Anodes for Lithium Ion Batteries with a Superhigh Capacity and Rate Capability
journal, March 2012


Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals
journal, March 2016

  • Liu, Yuanyue; Merinov, Boris V.; Goddard, William A.
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 14
  • DOI: 10.1073/pnas.1602473113

Vanadium Clustering/Declustering in P2–Na 1/2 VO 2 Layered Oxide
journal, February 2014

  • Guignard, Marie; Carlier, Dany; Didier, Christophe
  • Chemistry of Materials, Vol. 26, Issue 4
  • DOI: 10.1021/cm403114k

High Capacity of Hard Carbon Anode in Na-Ion Batteries Unlocked by PO x Doping
journal, July 2016


High capacity, reversible alloying reactions in SnSb/C nanocomposites for Na-ion battery applications
journal, January 2012

  • Xiao, Lifen; Cao, Yuliang; Xiao, Jie
  • Chemical Communications, Vol. 48, Issue 27
  • DOI: 10.1039/c2cc17129e

Amorphous TiO 2 Nanotube Anode for Rechargeable Sodium Ion Batteries
journal, September 2011

  • Xiong, Hui; Slater, Michael D.; Balasubramanian, Mahalingam
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 20
  • DOI: 10.1021/jz2012066

The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage
journal, February 2015

  • Kundu, Dipan; Talaie, Elahe; Duffort, Victor
  • Angewandte Chemie International Edition, Vol. 54, Issue 11
  • DOI: 10.1002/anie.201410376

High-Density Sodium and Lithium Ion Battery Anodes from Banana Peels
journal, June 2014

  • Lotfabad, Elmira Memarzadeh; Ding, Jia; Cui, Kai
  • ACS Nano, Vol. 8, Issue 7, p. 7115-7129
  • DOI: 10.1021/nn502045y

Polyanion-Type Electrode Materials for Sodium-Ion Batteries
journal, January 2017


Hard Carbon Originated from Polyvinyl Chloride Nanofibers As High-Performance Anode Material for Na-Ion Battery
journal, February 2015

  • Bai, Ying; Wang, Zhen; Wu, Chuan
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 9
  • DOI: 10.1021/acsami.5b00861

Carbon Nanosheet Frameworks Derived from Peat Moss as High Performance Sodium Ion Battery Anodes
journal, November 2013

  • Ding, Jia; Wang, Huanlei; Li, Zhi
  • ACS Nano, Vol. 7, Issue 12
  • DOI: 10.1021/nn404640c

MoS 2 /Graphene Composite Paper for Sodium-Ion Battery Electrodes
journal, January 2014

  • David, Lamuel; Bhandavat, Romil; Singh, Gurpreet
  • ACS Nano, Vol. 8, Issue 2
  • DOI: 10.1021/nn406156b

Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry
journal, May 2016

  • Ryder, Christopher R.; Wood, Joshua D.; Wells, Spencer A.
  • Nature Chemistry, Vol. 8, Issue 6
  • DOI: 10.1038/nchem.2505

A Hierarchical N/S-Codoped Carbon Anode Fabricated Facilely from Cellulose/Polyaniline Microspheres for High-Performance Sodium-Ion Batteries
journal, January 2016


A porous nitrogen and phosphorous dual doped graphene blocking layer for high performance Li–S batteries
journal, January 2015

  • Gu, Xingxing; Tong, Chuan-jia; Lai, Chao
  • Journal of Materials Chemistry A, Vol. 3, Issue 32
  • DOI: 10.1039/C5TA04255K

Superior Electrochemical Performance and Storage Mechanism of Na 3 V 2 (PO 4 ) 3 Cathode for Room-Temperature Sodium-Ion Batteries
journal, October 2012


Nitrogen-Doped Porous Carbon Nanosheets as Low-Cost, High-Performance Anode Material for Sodium-Ion Batteries
journal, December 2012


Sodium-Ion Batteries
journal, May 2012

  • Slater, Michael D.; Kim, Donghan; Lee, Eungje
  • Advanced Functional Materials, Vol. 23, Issue 8, p. 947-958
  • DOI: 10.1002/adfm.201200691

P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries
journal, April 2012

  • Yabuuchi, Naoaki; Kajiyama, Masataka; Iwatate, Junichi
  • Nature Materials, Vol. 11, Issue 6
  • DOI: 10.1038/nmat3309

Synthesis, Structure, and Electrochemical Properties of the Layered Sodium Insertion Cathode Material: NaNi 1 / 3 Mn 1 / 3 Co 1 / 3 O 2
journal, April 2012

  • Sathiya, M.; Hemalatha, K.; Ramesha, K.
  • Chemistry of Materials, Vol. 24, Issue 10
  • DOI: 10.1021/cm300466b

Is lithium the new gold?
journal, June 2010


High Capacity and Rate Capability of Amorphous Phosphorus for Sodium Ion Batteries
journal, March 2013

  • Qian, Jiangfeng; Wu, Xianyong; Cao, Yuliang
  • Angewandte Chemie International Edition, Vol. 52, Issue 17
  • DOI: 10.1002/anie.201209689

Sodium Ion Insertion in Hollow Carbon Nanowires for Battery Applications
journal, June 2012

  • Cao, Yuliang; Xiao, Lifen; Sushko, Maria L.
  • Nano Letters, Vol. 12, Issue 7
  • DOI: 10.1021/nl3016957

New Mechanistic Insights on Na-Ion Storage in Nongraphitizable Carbon
journal, August 2015


A high performance sulfur-doped disordered carbon anode for sodium ion batteries
journal, January 2015

  • Li, Wei; Zhou, Min; Li, Haomiao
  • Energy & Environmental Science, Vol. 8, Issue 10
  • DOI: 10.1039/C5EE01985K

Sulfur and nitrogen co-doped hollow carbon spheres for sodium-ion batteries with superior cyclic and rate performance
journal, January 2016

  • Ye, Jianchuan; Zang, Jun; Tian, Zhaowu
  • Journal of Materials Chemistry A, Vol. 4, Issue 34
  • DOI: 10.1039/C6TA04592H

The Mechanisms of Lithium and Sodium Insertion in Carbon Materials
journal, January 2001

  • Stevens, D. A.; Dahn, J. R.
  • Journal of The Electrochemical Society, Vol. 148, Issue 8
  • DOI: 10.1149/1.1379565

    Works referencing / citing this record:

    Freestanding N‐Doped Carbon Coated CuO Array Anode for Lithium‐Ion and Sodium‐Ion Batteries
    journal, May 2019


    Freestanding N‐Doped Carbon Coated CuO Array Anode for Lithium‐Ion and Sodium‐Ion Batteries
    journal, May 2019


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.