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Title: Mechanism of Na-Ion Storage in Hard Carbon Anodes Revealed by Heteroatom Doping

Abstract

Hard carbon is the candidate anode material for the commercialization of Na-ion batteries the batteries that by virtue of being constructed from inexpensive and abundant components open the door for massive scale up of battery-based storage of electrical energy. Holding back the development of these batteries is that a complete understanding of the mechanism of Na-ion storage in hard carbon has remained elusive. Although as an amorphous carbon, hard carbon possesses a subtle and complex structure composed of domains of layered rumpled sheets that have local order resembling graphene within each layer but complete disorder along the c-axis between layers. Here, we present two key discoveries: first that characteristics of hard carbon s structure can be modified systematically by heteroatom doping, and second, that these changes greatly affect Na-ion storage properties, which reveal the mechanisms for Na storage in hard carbon. Specifically, P, S and B doping was used to engineer the density of local defects in graphenic layers, and to modify the spacing between the layers. While opening the interlayer spacing through P or S doping extends the low-voltage capacity plateau, and increasing the defect concentration with P or B doping high first sodiation capacity is achieved. Furthermore, wemore » observe that the highly defective B-doped hard carbon suffers a tremendous irreversible capacity in the first desodiation cycle. Our combined first principles calculations and experimental studies revealed a new trapping mechanism, showing that the high binding energies between B-doping induced defects and Na-ions are responsible for the irreversible capacity. The understanding generated in this work provides a totally new set of guiding principles for materials engineers working to optimize hard carbon for Na-ion battery applications.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [1];  [4];  [1]
  1. Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
  3. Hewlett Packard Labs., Palo Alto, CA (United States)
  4. Univ. of California, Riverside, CA (United States). Materials Science and Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1361320
Alternate Identifier(s):
OSTI ID: 1393301
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 7; Journal Issue: 18; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; hard carbon anodes; heteroatom doping; local structures; mechanisms; Na-ion batteries

Citation Formats

Li, Zhifei, Bommier, Clement, Chong, Zhi Sen, Jian, Zelang, Surta, Todd Wesley, Wang, Xingfeng, Xing, Zhenyu, Neuefeind, Joerg C., Stickle, William F., Dolgos, Michelle, Greaney, P. Alex, and Ji, Xiulei. Mechanism of Na-Ion Storage in Hard Carbon Anodes Revealed by Heteroatom Doping. United States: N. p., 2017. Web. doi:10.1002/aenm.201602894.
Li, Zhifei, Bommier, Clement, Chong, Zhi Sen, Jian, Zelang, Surta, Todd Wesley, Wang, Xingfeng, Xing, Zhenyu, Neuefeind, Joerg C., Stickle, William F., Dolgos, Michelle, Greaney, P. Alex, & Ji, Xiulei. Mechanism of Na-Ion Storage in Hard Carbon Anodes Revealed by Heteroatom Doping. United States. doi:10.1002/aenm.201602894.
Li, Zhifei, Bommier, Clement, Chong, Zhi Sen, Jian, Zelang, Surta, Todd Wesley, Wang, Xingfeng, Xing, Zhenyu, Neuefeind, Joerg C., Stickle, William F., Dolgos, Michelle, Greaney, P. Alex, and Ji, Xiulei. Tue . "Mechanism of Na-Ion Storage in Hard Carbon Anodes Revealed by Heteroatom Doping". United States. doi:10.1002/aenm.201602894. https://www.osti.gov/servlets/purl/1361320.
@article{osti_1361320,
title = {Mechanism of Na-Ion Storage in Hard Carbon Anodes Revealed by Heteroatom Doping},
author = {Li, Zhifei and Bommier, Clement and Chong, Zhi Sen and Jian, Zelang and Surta, Todd Wesley and Wang, Xingfeng and Xing, Zhenyu and Neuefeind, Joerg C. and Stickle, William F. and Dolgos, Michelle and Greaney, P. Alex and Ji, Xiulei},
abstractNote = {Hard carbon is the candidate anode material for the commercialization of Na-ion batteries the batteries that by virtue of being constructed from inexpensive and abundant components open the door for massive scale up of battery-based storage of electrical energy. Holding back the development of these batteries is that a complete understanding of the mechanism of Na-ion storage in hard carbon has remained elusive. Although as an amorphous carbon, hard carbon possesses a subtle and complex structure composed of domains of layered rumpled sheets that have local order resembling graphene within each layer but complete disorder along the c-axis between layers. Here, we present two key discoveries: first that characteristics of hard carbon s structure can be modified systematically by heteroatom doping, and second, that these changes greatly affect Na-ion storage properties, which reveal the mechanisms for Na storage in hard carbon. Specifically, P, S and B doping was used to engineer the density of local defects in graphenic layers, and to modify the spacing between the layers. While opening the interlayer spacing through P or S doping extends the low-voltage capacity plateau, and increasing the defect concentration with P or B doping high first sodiation capacity is achieved. Furthermore, we observe that the highly defective B-doped hard carbon suffers a tremendous irreversible capacity in the first desodiation cycle. Our combined first principles calculations and experimental studies revealed a new trapping mechanism, showing that the high binding energies between B-doping induced defects and Na-ions are responsible for the irreversible capacity. The understanding generated in this work provides a totally new set of guiding principles for materials engineers working to optimize hard carbon for Na-ion battery applications.},
doi = {10.1002/aenm.201602894},
journal = {Advanced Energy Materials},
number = 18,
volume = 7,
place = {United States},
year = {2017},
month = {5}
}

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Works referenced in this record:

Boron-doped graphene as a promising anode for Na-ion batteries
journal, January 2014

  • Ling, Chen; Mizuno, Fuminori
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 22
  • DOI: 10.1039/C4CP01045K

Hard Carbon Microtubes Made from Renewable Cotton as High-Performance Anode Material for Sodium-Ion Batteries
journal, June 2016

  • Li, Yunming; Hu, Yong-Sheng; Titirici, Maria-Magdalena
  • Advanced Energy Materials, Vol. 6, Issue 18
  • DOI: 10.1002/aenm.201600659

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

Electrochemical Na Insertion and Solid Electrolyte Interphase for Hard-Carbon Electrodes and Application to Na-Ion Batteries
journal, August 2011

  • Komaba, Shinichi; Murata, Wataru; Ishikawa, Toru
  • Advanced Functional Materials, Vol. 21, Issue 20
  • DOI: 10.1002/adfm.201100854

Important Role of Functional Groups for Sodium Ion Intercalation in Expanded Graphite
journal, July 2015


Prototype Sodium-Ion Batteries Using an Air-Stable and Co/Ni-Free O3-Layered Metal Oxide Cathode
journal, October 2015


Ultra-Thick, Low-Tortuosity, and Mesoporous Wood Carbon Anode for High-Performance Sodium-Ion Batteries
journal, May 2016


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


N,P-Codoped Carbon Networks as Efficient Metal-free Bifunctional Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions
journal, December 2015


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

Mechanistic insights into sodium storage in hard carbon anodes using local structure probes
journal, January 2016

  • Stratford, Joshua M.; Allan, Phoebe K.; Pecher, Oliver
  • Chemical Communications, Vol. 52, Issue 84
  • DOI: 10.1039/C6CC06990H

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

General equation for the determination of the crystallite size La of nanographite by Raman spectroscopy
journal, April 2006

  • Cançado, L. G.; Takai, K.; Enoki, T.
  • Applied Physics Letters, Vol. 88, Issue 16
  • DOI: 10.1063/1.2196057

Carbon coated Na3V2(PO4)3 as novel electrode material for sodium ion batteries
journal, January 2012


Hydrothermal functionalization of ordered mesoporous carbons: The effect of boron on supercapacitor performance
journal, December 2015


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


Layer-by-Layer Na 3 V 2 (PO 4 ) 3 Embedded in Reduced Graphene Oxide as Superior Rate and Ultralong-Life Sodium-Ion Battery Cathode
journal, May 2016


Ionothermal synthesis of sulfur-doped porous carbons hybridized with graphene as superior anode materials for lithium-ion batteries
journal, January 2012

  • Yan, Yang; Yin, Ya-Xia; Xin, Sen
  • Chemical Communications, Vol. 48, Issue 86
  • DOI: 10.1039/c2cc36234a

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

Anode-Free Sodium Battery through in Situ Plating of Sodium Metal
journal, January 2017


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


Doping effect on the adsorption of Na atom onto graphenes
journal, May 2016


Local Atomic Density of Microporous Carbons
journal, January 2012

  • Dmowski, Wojtek; Contescu, Cristian I.; Llobet, Anna
  • The Journal of Physical Chemistry C, Vol. 116, Issue 4
  • DOI: 10.1021/jp209824f

A phosphorus/N-doped carbon nanofiber composite as an anode material for sodium-ion batteries
journal, January 2015

  • Ruan, Boyang; Wang, Jun; Shi, Dongqi
  • Journal of Materials Chemistry A, Vol. 3, Issue 37
  • DOI: 10.1039/C5TA04366B

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

Fluorine-Doped Carbon Particles Derived from Lotus Petioles as High-Performance Anode Materials for Sodium-Ion Batteries
journal, September 2015

  • Wang, Pengzi; Qiao, Bin; Du, Yichen
  • The Journal of Physical Chemistry C, Vol. 119, Issue 37
  • DOI: 10.1021/acs.jpcc.5b05443

Conversion of Lignin Precursors to Carbon Fibers with Nanoscale Graphitic Domains
journal, July 2014

  • Chatterjee, Sabornie; Jones, Eric B.; Clingenpeel, Amy C.
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 8
  • DOI: 10.1021/sc500189p

Hierarchical Carbon Framework Wrapped Na 3 V 2 (PO 4 ) 3 as a Superior High-Rate and Extended Lifespan Cathode for Sodium-Ion Batteries
journal, August 2015


Local structure of nanoporous carbons
journal, October 1999

  • Petkov, V.; Difrancesco, R. G.; Billinge, S. J. L.
  • Philosophical Magazine B, Vol. 79, Issue 10
  • DOI: 10.1080/13642819908218319

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

Nitrogen/phosphorus co-doped nonporous carbon nanofibers for high-performance supercapacitors
journal, February 2014


A Sustainable Route from Biomass Byproduct Okara to High Content Nitrogen-Doped Carbon Sheets for Efficient Sodium Ion Batteries
journal, November 2015


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


Expanded graphite as superior anode for sodium-ion batteries
journal, June 2014

  • Wen, Yang; He, Kai; Zhu, Yujie
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5033