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Transition-Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium- and Sodium-Ion Batteries with Excellent Cycling Properties

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [1];  [2];  [3];  [4];  [5];  [1];  [2];  [1]
  1. Inst. Charles Gerhardt de Montpellier, Montpellier (France); Electrochemical Energy Network Storage, Amiens (France)
  2. RWTH Aachen Univ. (Germany). Inst. of Inorganic Chemistry (IPC)
  3. Forschungszentrum Julich (Germany). Peter Grunberg Institute (PGI), Julich Centre for Neutron Science (JCNS); Univ. of Liege, (Belgium). Inst. of Chemistry
  4. Forschungszentrum Julich (Germany). Peter Grunberg Institute (PGI), Julich Centre for Neutron Science (JCNS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  5. Normandie Univ., Rouvray (France)
+ Show Author Affiliations
Here we report evidence for the electrochemical activity of transition-metal carbodiimides versus lithium and sodium. In particular, iron carbodiimide, FeNCN, can be efficiently used as a negative electrode material for alkali-metal-ion batteries, similar to its oxide analogue FeO. Based on 57Fe M ssbauer and infrared spectroscopy (IR) data, the electrochemical reaction mechanism can be explained by the reversible transformation of the Fe NCN into Li/Na NCN bonds during discharge and charge. These new electrode materials exhibit higher capacity compared to well-established negative electrode references such as graphite or hard carbon. Contrary to its oxide analogue, iron carbodiimide does not require heavy treatments (nanoscale tailoring, sophisticated textures, coating etc.) to obtain long cycle life with density current as high as 9 A/g-1 for hundreds of charge/discharge cycles. Similar to the iron compound, several other transition-metal carbodiimides Mx(NCN)y with M = Mn, Cr, Zn can cycle successfully versus lithium and sodium. Ultimately, their electrochemical activity and performances open the way to the design of a novel family of anode materials.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1261390
Alternate ID(s):
OSTI ID: 1401420
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 16 Vol. 55; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (55)

Crystal Structure Refinement of Lead Cyanamide and the Stiffness of the Cyanamide Anion journal January 2000
Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions journal August 2010
Research Progress on Negative Electrodes for Practical Li-Ion Batteries: Beyond Carbonaceous Anodes journal April 2015
Ein ferromagnetisches Carbodiimid: Cr2(NCN)3 journal May 2010
A Ferromagnetic Carbodiimide: Cr2(NCN)3 journal May 2010
FeNCN and Fe(NCNH) 2 : Synthesis, Structure, and Magnetic Properties of a Nitrogen-Based Pseudo-oxide and -hydroxide of Divalent Iron journal February 2009
A Theoretical Study on the Existence and Structures of Some Hypothetical First-Row Transition-Metal M(NCN) Compounds journal July 2005
Synthesis, Crystal Structure, and Properties of MnNCN, the First Carbodiimide of a Magnetic Transition Metal. journal July 2005
Synthesis, Crystal-Structure Determination and Magnetic Properties of Two New Transition-Metal Carbodiimides: CoNCN and NiNCN. journal June 2007
Dye-Mediated Growth of 2D Coppercarbodiimide (CuNCN) Nanostructures and their Metamorphosis into a 3D Cu@C x N y Hybrid journal January 2014
Experimental and Quantum-Chemical Investigations of the UV/Vis Absorption Spectrum of Manganese Carbodiimide, MnNCN journal February 2010
Unfolding the role of iron in Li-ion conversion electrode materials by 57Fe Mössbauer spectroscopy book January 2013
Unfolding the role of iron in Li-ion conversion electrode materials by 57Fe Mössbauer spectroscopy journal October 2011
A simple synthesis of MnN0.43@C nanocomposite: characterization and application as battery material journal December 2014
Functional groups in carbon black by FTIR spectroscopy journal January 1983
Syntheses, crystal structures, and vibrational spectroscopic properties of MgCN2, SrCN2, and BaCN2 journal May 1994
Incorporation of graphene into polyester/carbon nanofibers composites for better multi-stimuli responsive shape memory performances journal November 2013
On the high and low temperature performances of Na-ion battery materials: Hard carbon as a case study journal May 2015
Enhanced Electrochemical Stability of Sn-Carbon Nanotube Nanocapsules as Lithium-Ion Battery Anode journal October 2014
FeO/C anode materials of high capacity and cycle stability for lithium-ion batteries synthesized by carbothermal reduction journal July 2013
Adsorption and conformation of carboxymethyl cellulose at solid–liquid interfaces using spectroscopic, AFM and allied techniques journal November 2005
Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes journal April 2009
Lithium insertion/extraction mechanism in alloy anodes for lithium-ion batteries journal February 2011
Review on recent progress of nanostructured anode materials for Li-ion batteries journal July 2014
The Solid Electrolyte Interphase a key parameter of the high performance of Sb in sodium-ion batteries: Comparative X-ray Photoelectron Spectroscopy study of Sb/Na-ion and Sb/Li-ion batteries journal January 2015
Graphenothermal reduction synthesis of ‘exfoliated graphene oxide/iron (II) oxide’ composite for anode application in lithium ion batteries journal October 2015
Lithium-induced conversion reaction in wüstite Fe1−xO studied by 57Fe Mössbauer spectroscopy journal March 2012
Voltage Dependent Solid Electrolyte Interphase Formation in Silicon Electrodes: Monitoring the Formation of Organic Decomposition Products journal December 2015
Contribution of X-ray Photoelectron Spectroscopy to the Study of the Electrochemical Reactivity of CoO toward Lithium journal March 2004
Metal Oxides and Oxysalts as Anode Materials for Li Ion Batteries journal March 2013
Alloy Negative Electrodes for Li-Ion Batteries journal October 2014
Synthesis, Structure Determination, and Quantum-Chemical Characterization of an Alternate HgNCN Polymorph † journal August 2002
Synthesis, Crystal Structure, and Properties of MnNCN, the First Carbodiimide of a Magnetic Transition Metal † journal May 2005
Synthesis, Crystal-Structure Determination and Magnetic Properties of Two New Transition-Metal Carbodiimides:  CoNCN and NiNCN journal March 2007
Better Cycling Performances of Bulk Sb in Na-Ion Batteries Compared to Li-Ion Systems: An Unexpected Electrochemical Mechanism journal December 2012
Electronic Band Gap Reduction in Manganese Carbodiimide: MnNCN journal June 2013
Studies of the Interfacial Properties of an Electroplated Sn Thin Film Electrode/Electrolyte Using in Situ MFTIRS and EQCM journal December 2007
Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries journal September 2000
Magnetism and lattice dynamics of FeNCN compared to FeO journal January 2014
Photochemical and electrocatalytic water oxidation activity of cobalt carbodiimide journal January 2015
Carbodiimides: new materials applied as anode electrodes for sodium and lithium ion batteries journal January 2016
Metal organic frameworks for electrochemical applications journal January 2012
Synthesis of the dilithium salt of cyanamide in liquid lithium; X-ray crystal structure of Li2NCN journal January 1978
The reaction mechanism of FeSb2 as anode for sodium-ion batteries journal January 2014
High-resolution neutron diffraction study of CuNCN: New evidence of structure anomalies at low temperature journal December 2013
Determination of the magnetic structure of manganese carbodiimide with diffraction experiments using polarized neutrons journal July 2009
Unconventional Magnetism in a Nitrogen-Containing Analog of Cupric Oxide journal July 2011
Particle Size Effects on the Electrochemical Performance of Copper Oxides toward Lithium journal January 2001
On the Origin of the Extra Electrochemical Capacity Displayed by MO/Li Cells at Low Potential journal January 2002
In2.24(NCN)3 and NaIn(NCN)2: Synthesis and Crystal Structures of New Main Group Metal Cyanamides journal August 1995
Kristallstruktur und schwingungsspektroskopische Daten von Silbercyanamid / Crystal Structure and Spectroscopic Data of Silver Cyanamide journal May 2000
ATheoretical Study on the Existence and Structures of Some Hypothetical First-Row Transition-Metal M(NCN) Compounds journal April 2005
A Novel Method for Synthesizing Crystalline Copper Carbodiimide, CuNCN. Structure Determination by X-Ray Rietveld Refinement journal June 2005
Carbodiimides: new materials applied as anode electrodes for sodium and lithium ion batteries text January 2016
Photochemical and electrocatalytic water oxidation activity of cobalt carbodiimide text January 2015

Cited By (23)

Electrochemical Evaluation of Pb, Ag, and Zn Cyanamides/Carbodiimides journal February 2019
2D Nanospace Confined Synthesis of Pseudocapacitance-Dominated MoS 2 -in-Ti 3 C 2 Superstructure for Ultrafast and Stable Li/Na-Ion Batteries journal August 2018
Na-Ion Batteries for Large Scale Applications: A Review on Anode Materials and Solid Electrolyte Interphase Formation journal July 2017
Schwefel‐basierte Elektroden mit Mehrelektronenreaktionen für Raumtemperatur‐Natriumionenspeicherung journal July 2019
Quantum‐Chemical Study of the FeNCN Conversion‐Reaction Mechanism in Lithium‐ and Sodium‐Ion Batteries journal January 2020
Sulfur-Based Electrodes that Function via Multielectron Reactions for Room-Temperature Sodium-Ion Storage journal July 2019
Quantum‐Chemical Study of the FeNCN Conversion‐Reaction Mechanism in Lithium‐ and Sodium‐Ion Batteries journal January 2020
Cobalt Carbodiimide as Negative Electrode for Li‐Ion Batteries: Electrochemical Mechanism and Performance journal August 2019
Layered Carbodiimides A 2 M(CN 2 ) 3 with Tetravalent Cations M = Sn, Zr, and Hf : Layered Carbodiimides A journal April 2018
Reversible High Capacity and Reaction Mechanism of Cr 2 (NCN) 3 Negative Electrodes for Li‐Ion Batteries journal December 2019
Understanding Fundamentals and Reaction Mechanisms of Electrode Materials for Na-Ion Batteries journal January 2018
The Ternary Post-transition Metal Carbodiimide SrZn(NCN) 2 : The Ternary Post-transition Metal Carbodiimide SrZn(NCN) journal September 2017
Ammonothermal Synthesis of Alkali-Alkaline Earth Metal and Alkali-Rare Earth Metal Carbodiimides: K 5- x M x (CN 2 ) 2 +x (HCN 2 ) 1- x ( M = Sr, Eu) and Na 4.32 Sr 0.68 (CN 2 ) 2.68 (HCN 2 ) 0.32 : Ammonothermal Synthesis of Alkali-Alkaline Earth Metal and Alkali-Rare Earth Metal Carbodiimides: K5-xMx(CN2)2+x(HCN2)1-x (M = Sr, Eu) and Na4.32Sr0.6 journal October 2017
Nonaqueous synthesis of metal cyanamide semiconductor nanocrystals for photocatalytic water oxidation journal January 2018
Self-templated synthesis of heavily nitrogen-doped hollow carbon spheres journal January 2018
Carbodiimides as energy materials: which directions for a reasonable future? journal January 2018
Dual anode materials for lithium- and sodium-ion batteries journal January 2018
A new tilt and an old twist on the nickel arsenide structure-type: synthesis and characterisation of the quaternary transition-metal cyanamides A 2 MnSn 2 (NCN) 6 (A = Li and Na) journal January 2019
Quantum‐Chemical Study of the FeNCN Conversion‐Reaction Mechanism in Lithium‐ and Sodium‐Ion Batteries text January 2020
Quantum-Chemical Study of the FeNCN Conversion-Reaction Mechanism in Lithium- and Sodium-Ion Batteries text January 2020
Reversible High Capacity and Reaction Mechanism of Cr 2 (NCN) 3 Negative Electrodes for Li-Ion Batteries text January 2020
Synthesis, Crystal Structure, and Chemical-Bonding Analysis of BaZn(NCN)2 journal December 2017
Syntheses and Characterization of Two Dicyanamide Compounds Containing Monovalent Cations: Hg2[N(CN)2]2 and Tl[N(CN)2] journal December 2018

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Related Subjects

25 ENERGY STORAGE
batteries
carbodiimide
lithium ions
sodium ions