skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The Formation Mechanism of Fluorescent Metal Complexes at the LixNi0.5Mn1.5O4-δ/Carbonate Ester Electrolyte Interface

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja5116698· OSTI ID:1210596
 [1];  [1];  [2];  [1];  [3];  [3];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Illinois, Chicago, IL (United States)
  3. Univ. of Illinois, Chicago, IL (United States)
+ Show Author Affiliations

Electrochemical oxidation of carbonate esters at the LixNi0.5Mn1.5O4-δ/electrolyte interface results in Ni/Mn dissolution and surface film formation, which negatively affect the electrochemical performance of Li-ion batteries. Ex situ X-ray absorption (XRF/XANES), Raman, and fluorescence spectroscopy, along with imaging of LixNi0.5Mn1.5O4-δ positive and graphite negative electrodes from tested Li-ion batteries, reveal the formation of a variety of MnII/III and NiII complexes with β-diketonate ligands. These metal complexes, which are generated upon anodic oxidation of ethyl and diethyl carbonates at LixNi0.5Mn1.5O4-δ, form a surface film that partially dissolves in the electrolyte. The dissolved MnIII complexes are reduced to their MnII analogues, which are incorporated into the solid electrolyte interphase surface layer at the graphite negative electrode. This work elucidates possible reaction pathways and evaluates their implications for Li+ transport kinetics in Li-ion batteries.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
DOE Contract Number:
SC0001294
OSTI ID:
1210596
Journal Information:
Journal of the American Chemical Society, Vol. 137, Issue 10; Related Information: NECCES partners with Stony Brook University (lead); Argonne National Laboratory; Binghamton University; Brookhaven National University; University of California, San Diego; University of Cambridge, UK; Lawrence Berkeley National Laboratory; Massachusetts Institute of Technology; University of Michigan; Rutgers University
Country of Publication:
United States
Language:
English

References (46)

Positive Electrode Materials for Li-Ion and Li-Batteries † journal February 2010
Challenges for Rechargeable Li Batteries journal February 2010
The study of the anodic stability of alkyl carbonate solutions by in situ FTIR spectroscopy, EQCM, NMR and MS journal February 2001
The role of Li-ion battery electrolyte reactivity in performance decline and self-discharge journal June 2003
Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni0.2Li0.2Mn0.6]O2 journal June 2006
Understanding Transition-Metal Dissolution Behavior in LiNi 0.5 Mn 1.5 O 4 High-Voltage Spinel for Lithium Ion Batteries journal July 2013
Novel Lithium-Ion Cathode Materials Based on Layered Manganese Oxides journal July 2001
New insights into a high potential spinel and alkylcarbonate-based electrolytes journal February 2013
Issues and challenges facing rechargeable lithium batteries journal November 2001
Insertion Electrode Materials for Rechargeable Lithium Batteries journal July 1998
Electrochemical extraction of lithium from LiMn2O4 journal February 1984
Mn(II) deposition on anodes and its effects on capacity fade in spinel lithium manganate–carbon systems journal September 2013
Ultrathin Lithium-Ion Conducting Coatings for Increased Interfacial Stability in High Voltage Lithium-Ion Batteries journal May 2014
Manganese in Graphite Anode and Capacity Fade in Li Ion Batteries journal October 2014
Comparison of the Performance of LiNi1/2Mn3/2O4 with Different Microstructures journal January 2011
The effect of particle surface facets on the kinetic properties of LiMn 1.5 Ni 0.5 O 4 cathode materials journal January 2013
Composition-Structure Relationships in the Li-Ion Battery Electrode Material LiNi 0.5 Mn 1.5 O 4 journal August 2012
Lithium and sodium battery cathode materials: computational insights into voltage, diffusion and nanostructural properties journal January 2014
Surface structure and equilibrium particle shape of the LiMn 2 O 4 spinel from first-principles calculations journal February 2013
Oxygen Vacancies and Ordering of d-levels Control Voltage Suppression in Oxide Cathodes: the Case of Spinel LiNi 0.5 Mn 1.5 O 4- δ journal June 2013
High-Performance LiNi 0.5 Mn 1.5 O 4 Spinel Controlled by Mn 3+ Concentration and Site Disorder journal March 2012
Mechanisms and rate laws for oxygen exchange on mixed-conducting oxide surfaces journal January 2007
Oxide surfaces as environmental interfaces journal December 2003
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries journal September 2010
A review of conduction phenomena in Li-ion batteries journal December 2010
Breaking Bonds with Electrons and Protons. Models and Examples journal August 2013
Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy journal October 2012
Diagnostic Studies of Polyolefin Separators in High-Power Li-Ion Cells journal January 2004
Interfacial side-reactions at a LiNi0.5Mn1.5O4 electrode in organic carbonate-based electrolytes journal September 2013
Raman Microspectrometry Applied To The Study Of Electrode Materials For Lithium Batteries
  • Baddour-Hadjean, Rita; Pereira-Ramos, Jean-Pierre; Champion, P. M.
  • XXII INTERNATIONAL CONFERENCE ON RAMAN SPECTROSCOPY, AIP Conference Proceedings https://doi.org/10.1063/1.3482342
conference January 2010
Challenges Facing Lithium Batteries and Electrical Double-Layer Capacitors journal September 2012
Charge transfer to solvent identified using dark channel fluorescence-yield L-edge spectroscopy journal August 2010
Opportunities and challenges in single-molecule and single-particle fluorescence microscopy for mechanistic studies of chemical reactions journal November 2013
Charge-transfer-induced structural rearrangements at both sides of organic/metal interfaces journal March 2010
Combining In Situ Synchrotron X-Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium-Ion Batteries journal June 2012
Reactions of Tris(acetylacetonato)manganese(III) and Bis(acetylacetonato)-manganese(II) with Ethylenediamine and Other Primary Amines journal January 1972
Role of the support nature in chemisorption of Ni(acac)2 on the surface of silica and alumina journal July 1997
The Crystal and Molecular Structure of Bis(acetylacetonato)nickel (II) journal April 1965
Electronic structure and photoelectron spectra of nickel(II) acetylacetonate journal May 2013
Quantum Chemistry Studies of the Oxidative Stability of Carbonate, Sulfone and Sulfonate-Based Electrolytes Doped with BF conference January 2011
Crystal Surface and State of Charge Dependencies of Electrolyte Decomposition on LiMn 2 O 4 Cathode journal January 2014
Surface complexation and dissolution of hematite by C 1 -C 6 dicarboxylic acids at pH = 5.0 journal December 2001
Concerted proton-coupled electron transfers in aquo/hydroxo/oxo metal complexes: Electrochemistry of [OsII(bpy)2py(OH2)]2+ in water journal July 2009
Anodic and Cathodic CC-Bond Formation journal November 1981
Microscopic Observations of Reductive Manganite Dissolution under Oxic Conditions journal June 2003
The Impact of Electrolyte Oxidation Products in LiNi 0.5 Mn 1.5 O 4 /Li 4 Ti 5 O 12 Cells journal January 2013

Similar Records

Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi0.5Mn1.5O4 Electrodes
Journal Article · Wed Nov 11 00:00:00 EST 2015 · Journal of Physical Chemistry. C · OSTI ID:1210596
+3 more
A study of room-temperature LixMn1.5Ni0.5O4 solid solutions
Journal Article · Mon Jan 26 00:00:00 EST 2015 · Scientific Reports · OSTI ID:1210596
+1 more
Electrode behavior RE-visited: Monitoring potential windows, capacity loss, and impedance changes in Li1.03 (Ni0.5Co0.2Mn0.3)0.97O2/silicon-graphite full cells
Journal Article · Fri Mar 04 00:00:00 EST 2016 · Journal of the Electrochemical Society · OSTI ID:1210596
+4 more

Related Subjects

energy storage (including batteries and capacitors)
defects
charge transport
materials and chemistry by design
synthesis (novel materials)