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Title: High‐Temperature Treatment of Li‐Rich Cathode Materials with Ammonia: Improved Capacity and Mean Voltage Stability during Cycling

Journal Article · · Advanced Energy Materials
ORCiD logo [1];  [1];  [1];  [2];  [1];  [1];  [3];  [1];  [1];  [4];  [5];  [5];  [1];  [2];  [1]
  1. Department of Chemistry Faculty of Exact Sciences Bar‐Ilan University Ramat‐Gan 5290002 Israel
  2. Department of Materials Science and Chemical Engineering Stony Brook University Stony Brook NY 11794 USA
  3. Wolfson Applied Materials Research Center Tel‐Aviv University Tel‐Aviv 69978 Israel
  4. Department of Materials Engineering Ben Gurion University of the Negev Beer‐Sheva 8410501 Israel
  5. BASF SE 67063 Ludwigshafen am Rhein Rheinland‐Pfalz Germany
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Li‐rich electrode materials of the family x Li 2 MnO 3 ·(1− x )LiNi a Co b Mn c O 2 ( a + b + c = 1) suffer a voltage fade upon cycling that limits their utilization in commercial batteries despite their extremely high discharge capacity, ≈250 mA h g −1 . Li‐rich, 0.35Li 2 MnO 3 ·0.65LiNi 0.35 Mn 0.45 Co 0.20 O 2 , is exposed to NH 3 at 400 °C, producing materials with improved characteristics: enhanced electrode capacity and a limited average voltage fade during 100 cycles in half cells versus Li. Three main changes caused by NH 3 treatment are established. First, a general bulk reduction of Co and Mn is observed via X‐ray photoelectron spectroscopy and X‐ray absorption near edge structure. Next, a structural rearrangement lowers the coordination number of CoO and MnO bonds, as well as formation of a surface spinel‐like structure. Additionally, Li + removal from the bulk causes the formation of surface LiOH, Li 2 CO 3 , and Li 2 O. These structural and surface changes can enhance the voltage and capacity stability of the Li‐rich material electrodes after moderate NH 3 treatment times of 1–2 h.

Sponsoring Organization:
USDOE
Grant/Contract Number:
DE‐AC02‐06CH11357
OSTI ID:
1393303
Journal Information:
Advanced Energy Materials, Journal Name: Advanced Energy Materials Vol. 7 Journal Issue: 18; ISSN 1614-6832
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English
Citation Metrics:
Cited by: 141 works
Citation information provided by
Web of Science

References (70)

Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes: I. Nickel-Rich, LiNi journal December 2016
Understanding the Rate Capability of High-Energy-Density Li-Rich Layered Li 1.2 Ni 0.15 Co 0.1 Mn 0.55 O 2 Cathode Materials journal December 2013
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes journal July 2013
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal June 2005
XANES study of electronic and structural nature of Mn-sites in manganese oxides with catalytic properties journal October 2005
Structural and electrochemical analysis of layered compounds from Li2MnO3 journal September 1999
Li + -Ion Extraction/Insertion of Ni-Rich Li 1+ x (Ni y Co z Mn z ) w O 2 (0.005< x <0.03; y : z =8:1, w ≈1) Electrodes: In Situ XRD and Raman Spectroscopy Study journal July 2015
A new approach to improve the high-voltage cyclic performance of Li-rich layered cathode material by electrochemical pre-treatment journal August 2008
A new variety of LiMnO2 with a layered structure journal August 1996
New Horizons for Conventional Lithium Ion Battery Technology journal September 2014
The impact of upper cut-off voltages on the electrochemical behaviors of composite electrode 0.3Li2MnO3·0.7LiMn1/3Ni1/3Co1/3O2 journal January 2012
Thermal Stability of Li 2 O 2 and Li 2 O for Li-Air Batteries: In Situ XRD and XPS Studies journal January 2013
K -edge absorption spectra of selected vanadium compounds journal November 1984
X-ray Photoemission Spectroscopy Study of Cationic and Anionic Redox Processes in High-Capacity Li-Ion Battery Layered-Oxide Electrodes journal January 2016
Understanding the Roles of Anionic Redox and Oxygen Release during Electrochemical Cycling of Lithium-Rich Layered Li 4 FeSbO 6 journal April 2015
The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries journal January 2016
Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries
  • Thackeray, Michael M.; Johnson, Christopher S.; Vaughey, John T.
  • Journal of Materials Chemistry, Vol. 15, Issue 23, p. 2257-2267 https://doi.org/10.1039/b417616m
journal March 2005
Effect of cycling conditions on the electrochemical performance of high capacity Li and Mn-rich cathodes for Li-ion batteries journal June 2016
Electrochemical Cyclability of Orthorhombic LiMnO[sub 2] journal January 1997
Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction journal May 2013
Origin of voltage decay in high-capacity layered oxide electrodes journal December 2014
A high rate Li-rich layered MNC cathode material for lithium-ion batteries journal January 2015
High resolution XPS of organic polymers, the scienta ESCA300 database. By G. Beamson and D. Briggs, Wiley, Chichester 1992, 295 pp., hardcover, £ 65.00, ISBN 0-471-93592-1 journal October 1993
Electrochemistry and Structural Chemistry of LiNiO[sub 2] (R3m) for 4 Volt Secondary Lithium Cells journal January 1993
Surface nitridation of Li-rich layered Li(Li0.17Ni0.25Mn0.58)O2 oxide as cathode material for lithium-ion battery journal January 2012
Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries journal June 1996
Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries journal December 2015
Lithium metal rechargeable cells using Li2MnO3 as the positive electrode journal July 1999
Formation of a linear LiOH compound on Cu(001): reaction of H2O with Li adatoms at low coverages journal March 1992
Structural and Electrochemical Evidence of Layered to Spinel Phase Transformation of Li and Mn Rich Layered Cathode Materials of the Formulae xLi[Li 1/3 Mn 2/3 ]O 2 .(1-x)LiMn 1/3 Ni 1/3 Co 1/3 O 2 (x = 0.2, 0.4, 0.6) upon Cycling journal January 2014
New interpretations of XPS spectra of nickel metal and oxides journal May 2006
Preparation and characterization of o-LiMnO2 cathode materials journal March 2007
Layered Li(Li0.2Ni0.15+0.5zCo0.10Mn0.55−0.5z)O2−zFz cathode materials for Li-ion secondary batteries journal August 2005
Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni journal January 2011
First Evidence of Manganese–Nickel Segregation and Densification upon Cycling in Li-Rich Layered Oxides for Lithium Batteries journal July 2013
In Situ X-Ray Absorption Near-Edge Structure Evidence for Quadrivalent Nickel in Nickel Battery Electrodes journal January 1996
High Capacity, Surface-Modified Layered Li [Li (1−x) ∕ 3Mn (2−x) ∕ 3Nix ∕ 3Cox ∕ 3 ] O2 Cathodes with Low Irreversible Capacity Loss journal March 2006
Electrochemical and Structural Properties of xLi2M‘O3 ·(1− x )LiMn0.5Ni0.5O2 Electrodes for Lithium Batteries (M‘ = Ti, Mn, Zr; 0 ≤ x ⩽ 0.3) journal May 2004
Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes: II. Lithium-Rich, xLi journal January 2017
Understanding the Anomalous Capacity of Li / Li [ NixLi ( 1 / 3 − 2x / 3 ) Mn ( 2 / 3 − x / 3 ) ]  O2 Cells Using In Situ X-Ray Diffraction and Electrochemical Studies journal January 2002
Probing the Degradation Mechanism of Li 2 MnO 3 Cathode for Li-Ion Batteries journal January 2015
Reversible Li-Intercalation through Oxygen Reactivity in Li-Rich Li-Fe-Te Oxide Materials journal January 2015
Integrated Materials xLi[sub 2]MnO[sub 3]⋅(1−x)LiMn[sub 1/3]Ni[sub 1/3]Co[sub 1/3]O[sub 2] (x=0.3, 0.5, 0.7) Synthesized journal January 2010
Review—Li-Rich Layered Oxide Cathodes for Next-Generation Li-Ion Batteries: Chances and Challenges journal January 2015
Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes journal August 2013
A brief review: Past, present and future of lithium ion batteries journal December 2016
The effect of ammonia reduction on the spinel electrode materials, LiMn2O4 and Li(LiMn)O4 journal October 1994
XPS Investigation of Surface Reactivity of Electrode Materials: Effect of the Transition Metal journal March 2015
Surface Characterization of Electrodes from High Power Lithium-Ion Batteries journal January 2002
Studies of Aluminum-Doped LiNi 0.5 Co 0.2 Mn 0.3 O 2 : Electrochemical Behavior, Aging, Structural Transformations, and Thermal Characteristics journal January 2015
Quantifying Hysteresis and Voltage Fade in xLi 2 MnO 3 ● (1-x)LiMn 0.5 Ni 0.5 O 2 Electrodes as a Function of Li 2 MnO 3 Content journal December 2013
Studies of Li and Mn-Rich Li x [MnNiCo]O 2 Electrodes: Electrochemical Performance, Structure, and the Effect of the Aluminum Fluoride Coating journal January 2013
Cation order/disorder in lithium transition-metal oxides as insertion electrodes for lithium-ion batteries journal January 2002
XPS analysis of a lithium surface immersed in propylene carbonate solution containing various salts journal July 1992
Factors that affect Li mobility in layered lithium transition metal oxides journal September 2006
Anomalous capacity and cycling stability of xLi2MnO3·(1−x)LiMO2 electrodes (M=Mn, Ni, Co) in lithium batteries at 50°C journal April 2007
Enhanced capacity and lower mean charge voltage of Li-rich cathodes for lithium ion batteries resulting from low-temperature electrochemical activation journal January 2017
Role of Electronic Structure in the Susceptibility of Metastable Transition-Metal Oxide Structures to Transformation journal October 2004
Countering the Voltage Decay in High Capacity xLi 2 MnO 3 •(1–x)LiMO 2 Electrodes (M=Mn, Ni, Co) for Li + -Ion Batteries journal January 2012
Mechanism of ammonia oxidation over oxides studied by temporal analysis of products journal September 2007
Li–O 2 Battery Degradation by Lithium Peroxide (Li 2 O 2 ): A Model Study journal December 2012
Study of the electrochemical behavior of the “inactive” Li2MnO3 journal September 2012
IFEFFIT  : interactive XAFS analysis and FEFF fitting journal March 2001
Synthesis, Characterization and Electrochemistry of Lithium Battery Electrodes: x Li 2 MnO 3 ·(1 − x )LiMn 0.333 Ni 0.333 Co 0.333 O 2 (0 ≤ x ≤ 0.7) journal October 2008
Lithium manganese oxides from Li2MnO3 for rechargeable lithium battery applications journal June 1991
High-energy ‘composite’ layered manganese-rich cathode materials via controlling Li2MnO3 phase activation for lithium-ion batteries journal January 2012
On the Surface Chemistry of LiMO[sub 2] Cathode Materials (M=[MnNi] and [MnNiCo]): Electrochemical, Spectroscopic, and Calorimetric Studies journal January 2010
Relationship between Electrochemical Pre-Treatment and Cycle Performance of a Li-Rich Solid-Solution Layered Li1^|^minus;^|^alpha;[Ni0.18Li0.20+^|^alpha;Co0.03Mn0.58]O2 Cathode for Li-Ion Secondary Batteries journal January 2012
Layered Lithium Insertion Material of LiCo 1/3 Ni 1/3 Mn 1/3 O 2 for Lithium-Ion Batteries journal July 2001
In situ X-ray diffraction study of the lithium excess layered oxide compound Li[Li0.2Ni0.2Mn0.6]O2 during electrochemical cycling journal January 2012

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