Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery

Journal Article · · Nature Communications
 [1];  [2];  [2];  [3];  [4];  [2];  [2];  [2];  [2];  [4];  [2];  [2];  [4];  [2];  [2];  [5];  [6];  [4];  [7]
  1. Peking Univ., Shenzhen (China); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Illinois, Chicago, IL (United States)
  4. Peking Univ., Shenzhen (China)
  5. Univ. of Illinois, Chicago, IL (United States)
  6. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  7. Argonne National Lab. (ANL), Argonne, IL (United States); Stanford Univ., CA (United States); Imam Abdulrahman Bin Faisal Univ. (IAU), Dammam (Saudi Arabia)
+ Show Author Affiliations
Historically long accepted to be the singular root cause of capacity fading, transition metal dissolution has been reported to severely degrade the anode. However, its impact on the cathode behavior remains poorly understood. Here we show the correlation between capacity fading and phase/surface stability of an LiMn2O4 cathode. It is revealed that a combination of structural transformation and transition metal dissolution dominates the cathode capacity fading. LiMn2O4 exhibits irreversible phase transitions driven by manganese(III) disproportionation and Jahn-Teller distortion, which in conjunction with particle cracks results in serious manganese dissolution. Meanwhile, fast manganese dissolution in turn triggers irreversible structural evolution, and as such, forms a detrimental cycle constantly consuming active cathode components. Furthermore, lithium-rich LiMn2O4 with lithium/manganese disorder and surface reconstruction could effectively suppress the irreversible phase transition and manganese dissolution. These findings close the loop of understanding capacity fading mechanisms and allow for development of longer life batteries.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Key Research and Development Program of China; National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1607377
Journal Information:
Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 10; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

References (59)

30 Years of Lithium-Ion Batteries journal June 2018
Origin of self-discharge mechanism in LiMn2O4-based Li-ion cells: A chemical and electrochemical approach journal September 1997
High-Energy Synchrotron X-Ray Diffraction and Its Application to In Situ Structural Phase-Transition Studies in Complex Sample Environments journal January 2012
Preparation of a new crystal form of manganese dioxide: λ-MnO2 journal September 1981
Structure refinement of the spinel-related phases Li2Mn2O4 and Li0.2Mn2O4 journal April 1987
Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells journal April 1994
Stabilization of a High-Capacity and High-Power Nickel-Based Cathode for Li-Ion Batteries journal April 2018
Li-ion battery materials: present and future journal June 2015
Manganese oxides for lithium batteries journal January 1997
Ni/Li Disordering in Layered Transition Metal Oxide: Electrochemical Impact, Origin, and Control journal June 2019
Surface Structure, Morphology, and Stability of Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 Cathode Material journal April 2017
LiMn 2 O 4 Surface Chemistry Evolution during Cycling Revealed by in Situ Auger Electron Spectroscopy and X-ray Photoelectron Spectroscopy journal April 2017
Microwave-Assisted Synthesis of High-Voltage Nanostructured LiMn1.5Ni0.5O4 Spinel: Tuning the Mn3+ Content and Electrochemical Performance journal July 2013
Spongelike Nanosized Mn 3 O 4 as a High-Capacity Anode Material for Rechargeable Lithium Batteries journal July 2011
Surface Structure Evolution of LiMn 2 O 4 Cathode Material upon Charge/Discharge journal May 2014
Ultimate Limits to Intercalation Reactions for Lithium Batteries journal October 2014
Dynamic Structural Changes at LiMn 2 O 4 /Electrolyte Interface during Lithium Battery Reaction journal November 2010
The Li-Ion Rechargeable Battery: A Perspective journal January 2013
High Performance LiMn 2 O 4 Cathode Materials Grown with Epitaxial Layered Nanostructure for Li-Ion Batteries journal January 2014
Synthesis of Single Crystalline Spinel LiMn 2 O 4 Nanowires for a Lithium Ion Battery with High Power Density journal March 2009
Building better batteries journal February 2008
Promise and reality of post-lithium-ion batteries with high energy densities journal March 2016
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries journal March 2014
The role of nanotechnology in the development of battery materials for electric vehicles journal December 2016
Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release journal July 2018
Effect of excess lithium in LiMn 2 O 4 and Li 1.15 Mn 1.85 O 4 electrodes revealed by quantitative analysis of soft X-ray absorption spectroscopy journal February 2017
Spinel Electrodes for Lithium Batteries journal December 1999
Correlating Capacity Fading and Structural Changes in Li[sub 1+y]Mn[sub 2−y]O[sub 4−δ] Spinel Cathode Materials: A Systematic Study on the Effects of Li/Mn Ratio and Oxygen Deficiency journal January 2001
Capacity Fading on Cycling of 4 V Li∕LiMn[sub 2]O[sub 4] Cells journal January 1997
Impact of 2-Vinylpyridine as Electrolyte Additive on Surface and Electrochemistry of Graphite for C∕LiMn[sub 2]O[sub 4] Li-Ion Cells journal January 2005
Comparison of Metal Ion Dissolutions from Lithium Ion Battery Cathodes journal January 2006
Review—Manganese Dissolution from Spinel Cathode: Few Unanswered Questions journal December 2016
Tuning the Mn Deposition on the Anode to Improve the Cycle Performance of the Mn-Based Lithium Ion Battery journal April 2017
First Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li(x)Mn(2)O(4) (100) Surfaces text January 2012
First Principles Modeling of Mn(II) Migration above and Dissolution from Li(x)Mn(2)O(4) (001) Surfaces text January 2017
Tuning the Mn Deposition on the Anode to Improve the Cycle Performance of the Mn-Based Lithium Ion Battery journal February 2016
Origin of self-discharge mechanism in LiMn2O4-based Li-ion cells: A chemical and electrochemical approach journal September 1997
LiMn2O4 for 4 V lithium-ion batteries journal September 1995
Structural transition in Mg-doped LiMn2O4: a comparison with other M-doped Li–Mn spinels journal January 2003
Manganese oxides for lithium batteries journal January 1997
The LiMn2O4 to λ-MnO2 phase transition studied by in situ neutron diffraction journal September 2001
Neutron diffraction study of electrochemically delithiated LiMn2O4 spinel journal November 1999
Study of Mn dissolution from LiMn2O4 spinel electrodes using in situ total reflection X-ray fluorescence analysis and fluorescence XAFS technique journal July 2001
First-Principles Modeling of Mn(II) Migration above and Dissolution from Li x Mn 2 O 4 (001) Surfaces journal November 2016
Mn3O4−Graphene Hybrid as a High-Capacity Anode Material for Lithium Ion Batteries journal October 2010
On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions journal January 2017
First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li x Mn 2 O 4 (100) Surfaces journal April 2012
Understanding Transition-Metal Dissolution Behavior in LiNi 0.5 Mn 1.5 O 4 High-Voltage Spinel for Lithium Ion Batteries journal July 2013
Manganese in Graphite Anode and Capacity Fade in Li Ion Batteries journal October 2014
Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries journal April 2017
Mn(II) deposition on anodes and its effects on capacity fade in spinel lithium manganate–carbon systems journal September 2013
Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox journal December 2017
In situ quantification of interphasial chemistry in Li-ion battery journal November 2018
Dissolution, migration, and deposition of transition metal ions in Li-ion batteries exemplified by Mn-based cathodes – a critical review journal January 2018
Electronic structure and stability of the LixMn2O4 (0 < x < 2) system journal January 1999
Challenges in the development of advanced Li-ion batteries: a review journal January 2011
Structural Changes of LiMn[sub 2]O[sub 4] Spinel Electrodes during Electrochemical Cycling journal January 1999
Dissolution of Spinel Oxides and Capacity Losses in 4V Li / LixMn2O4 Cells journal January 1996
Influence of Manganese Dissolution on the Degradation of Surface Films on Edge Plane Graphite Negative-Electrodes in Lithium-Ion Batteries journal January 2012

Similar Records

Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach
Journal Article · Mon Dec 15 23:00:00 EST 2014 · Nature Communications · OSTI ID:1210455
Phase transition of LiMn{sub 2}O{sub 4} spinel and its application for lithium ion secondary battery
Conference · Wed Jul 01 00:00:00 EDT 1998 · OSTI ID:20019154
An investigation of capacity fading of manganese spinels stored at elevated temperature
Journal Article · Sat Oct 31 23:00:00 EST 1998 · Journal of the Electrochemical Society · OSTI ID:289415

Related Subjects

25 ENERGY STORAGE