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

Journal Article · · Advanced Energy Materials
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  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
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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.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Organization:
USDOE Office of Science (SC); National Science Foundation (NSF)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1361320
Alternate ID(s):
OSTI ID: 1393301
Journal Information:
Advanced Energy Materials, Vol. 7, Issue 18; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 290 works
Citation information provided by
Web of Science

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Cited By (57)

Understanding of the Ultrastable K-Ion Storage of Carbonaceous Anode journal May 2018
Nickel Chelate Derived NiS 2 Decorated with Bifunctional Carbon: An Efficient Strategy to Promote Sodium Storage Performance journal August 2018
Sodium Storage and Electrode Dynamics of Tin–Carbon Composite Electrodes from Bulk Precursors for Sodium‐Ion Batteries journal February 2019
Graphitic Nanocarbon with Engineered Defects for High‐Performance Potassium‐Ion Battery Anodes journal June 2019
A Nonaqueous Potassium-Based Battery-Supercapacitor Hybrid Device journal March 2018
Rational Design and General Synthesis of S-Doped Hard Carbon with Tunable Doping Sites toward Excellent Na-Ion Storage Performance journal May 2018
Self‐Supporting, Flexible, Additive‐Free, and Scalable Hard Carbon Paper Self‐Interwoven by 1D Microbelts: Superb Room/Low‐Temperature Sodium Storage and Working Mechanism journal August 2019
Sodium/Potassium‐Ion Batteries: Boosting the Rate Capability and Cycle Life by Combining Morphology, Defect and Structure Engineering journal January 2020
Design and Synthesis of Layered Na 2 Ti 3 O 7 and Tunnel Na 2 Ti 6 O 13 Hybrid Structures with Enhanced Electrochemical Behavior for Sodium-Ion Batteries journal July 2018
Direct Structure–Performance Comparison of All‐Carbon Potassium and Sodium Ion Capacitors journal April 2019
Elucidation of the Sodium-Storage Mechanism in Hard Carbons journal February 2018
From Charge Storage Mechanism to Performance: A Roadmap toward High Specific Energy Sodium-Ion Batteries through Carbon Anode Optimization journal March 2018
Pristine or Highly Defective? Understanding the Role of Graphene Structure for Stable Lithium Metal Plating journal November 2018
Carbon Anodes for Nonaqueous Alkali Metal‐Ion Batteries and Their Thermal Safety Aspects journal August 2019
In Situ Revealing the Electroactivity of PO and PC Bonds in Hard Carbon for High‐Capacity and Long‐Life Li/K‐Ion Batteries journal July 2019
Slope‐Dominated Carbon Anode with High Specific Capacity and Superior Rate Capability for High Safety Na‐Ion Batteries journal February 2019
Bullet‐like Cu 9 S 5 Hollow Particles Coated with Nitrogen‐Doped Carbon for Sodium‐Ion Batteries journal May 2019
Multiple Active Sites of Carbon for High‐Rate Surface‐Capacitive Sodium‐Ion Storage journal August 2019
Slope-Dominated Carbon Anode with High Specific Capacity and Superior Rate Capability for High Safety Na-Ion Batteries journal February 2019
Bullet‐like Cu 9 S 5 Hollow Particles Coated with Nitrogen‐Doped Carbon for Sodium‐Ion Batteries journal June 2019
Multiple Active Sites of Carbon for High‐Rate Surface‐Capacitive Sodium‐Ion Storage journal September 2019
Carbon and Carbon Hybrid Materials as Anodes for Sodium-Ion Batteries journal April 2018
Self-Polymerized Disordered Carbon Enabling High Sodium Storage Performance through Expanded Interlayer Spacing by Bound Sulfur Atoms journal August 2018
Facile Synthesis of Ultra‐Small Few‐Layer Nanostructured MoSe 2 Embedded on N, P Co‐Doped Bio‐Carbon for High‐Performance Half/Full Sodium‐Ion and Potassium‐Ion Batteries journal September 2019
Hard Carbons for Sodium-Ion Battery Anodes: Synthetic Strategies, Material Properties, and Storage Mechanisms journal January 2018
Impact of the Acid Treatment on Lignocellulosic Biomass Hard Carbon for Sodium-Ion Battery Anodes journal July 2018
Hard Carbon as Sodium‐Ion Battery Anodes: Progress and Challenges journal November 2018
Carbonaceous Anodes Derived from Sugarcane Bagasse for Sodium‐Ion Batteries journal April 2019
Superior Cycling Stability and Fast Reaction Kinetics of NaV 2.9 Mg 0.1 (PO 4 ) 3 /C Anode for Sodium‐Ion Batteries journal August 2019
Catalytic Synthesis of Hard/Soft Carbon Hybrids with Heteroatom Doping for Enhanced Sodium Storage journal March 2019
Recent Advances of Cellulose-Based Materials and Their Promising Application in Sodium-Ion Batteries and Capacitors journal September 2018
A Functionalized Carbon Surface for High‐Performance Sodium‐Ion Storage journal August 2019
Heteroatom‐Doped Carbon Materials: Synthesis, Mechanism, and Application for Sodium‐Ion Batteries journal October 2018
Low-content Ni-doped CoS2 embedded within N,P-codoped biomass-derived carbon spheres for enhanced lithium/sodium storage journal February 2019
Low-cost lignite-derived hard carbon for high-performance sodium-ion storage journal February 2020
Realizing simultaneously enhanced energy and power density full-cell construction using mixed hard carbon/Li4Ti5O12 electrode journal July 2019
A Perspective: the Technical Barriers of Zn Metal Batteries journal January 2020
Bimetal-organic-framework derived CoTiO3 mesoporous micro-prisms anode for superior stable power sodium ion batteries journal February 2018
Recent progress and future prospects of sodium-ion capacitors journal November 2019
High valence Mo-doped Na 3 V 2 (PO 4 ) 3 /C as a high rate and stable cycle-life cathode for sodium battery journal January 2018
Porous NaV 3 (PO 4 ) 3 /C nanocomposite anode with superior Na-storage performance for sodium-ion batteries journal January 2019
Tunable porous carbon spheres for high-performance rechargeable batteries journal January 2018
Evaluating the influences of the sulfur content in precursors on the structure and sodium storage performances of carbon materials journal January 2018
Facile synthesis of N,O-codoped hard carbon on the kilogram scale for fast capacitive sodium storage journal January 2018
Hierarchical N/S co-doped carbon anodes fabricated through a facile ionothermal polymerization for high-performance sodium ion batteries journal January 2019
Engineering doping-vacancy double defects and insights into the conversion mechanisms of an Mn–O–F ultrafine nanowire anode for enhanced Li/Na-ion storage and hybrid capacitors journal January 2019
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Research Update: Hard carbon with closed pores from pectin-free apple pomace waste for Na-ion batteries journal April 2018
Phosphorus-doped hollow carbon sphere derived from phytic acid for superior sodium-ion batteries journal July 2018
Sodium storage properties of thin phosphorus-doped graphene layers developed on the surface of nanodiamonds under hot pressing conditions journal January 2020
Research Update : Hard carbon with closed pores from pectin-free apple pomace waste for Na-ion batteries text January 2018
Nutty Carbon: Morphology Replicating Hard Carbon from Walnut Shell for Na Ion Battery Anode journal July 2017

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Related Subjects

36 MATERIALS SCIENCE
25 ENERGY STORAGE
hard carbon anodes
heteroatom doping
local structures
mechanisms
Na-ion batteries