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
 

Fictitious phase separation in Li layered oxides driven by electro-autocatalysis

Journal Article · · Nature Materials
 [1];  [2];  [3];  [4];  [3];  [5];  [2];  [5];  [6];  [7];  [8];  [9]
  1. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering
  3. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
  4. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); SLAC National Accelerator Lab., Menlo Park, CA (United States). Applied Energy Div.
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  6. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); SLAC National Accelerator Lab., Menlo Park, CA (United States). Applied Energy Div.; Korea Institute of Science and Technology, Seoul (Korea, Republic of)
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); SLAC National Accelerator Lab., Menlo Park, CA (United States). Applied Energy Div.
  8. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering; Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Mathematics
  9. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES); SLAC National Accelerator Lab., Menlo Park, CA (United States). Applied Energy Div.
+ Show Author Affiliations

Layered oxides widely used as lithium-ion battery electrodes are designed to be cycled under conditions that avoid phase transitions. Although the desired single-phase composition ranges are well established near equilibrium, operando diffraction studies on many-particle porous electrodes have suggested phase separation during delithiation. Notably, the separation is not always observed, and never during lithiation. These anomalies have been attributed to irreversible processes during the first delithiation or reversible concentration-dependent diffusion. However, these explanations are not consistent with all experimental observations such as rate and path dependencies and particle-by-particle lithium concentration changes. Here, we show that the apparent phase separation is a dynamical artefact occurring in a many-particle system driven by autocatalytic electrochemical reactions, that is, an interfacial exchange current that increases with the extent of delithiation. We experimentally validate this population-dynamics model using the single-phase material Lix(Ni1/3Mn1/3Co1/3)O2 (0.5 < x < 1) and demonstrate generality with other transition-metal compositions. Operando diffraction and nanoscale oxidation-state mapping unambiguously prove that this fictitious phase separation is a repeatable non-equilibrium effect. We quantitatively confirm the theory with multiple-datastream-driven model extraction. More generally, our study experimentally demonstrates the control of ensemble stability by electro-autocatalysis, highlighting the importance of population dynamics in battery electrodes (even non-phase-separating ones).

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1781587
Journal Information:
Nature Materials, Journal Name: Nature Materials Journal Issue: 7 Vol. 8235; ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

References (41)

Modern Thermodynamics book November 2014
Persistent State-of-Charge Heterogeneity in Relaxed, Partially Charged Li 1− x Ni 1/3 Co 1/3 Mn 1/3 O 2 Secondary Particles journal May 2016
Lithium‐Battery Anode Gains Additional Functionality for Neuromorphic Computing through Metal–Insulator Phase Separation journal January 2020
High-Rate Charging Induced Intermediate Phases and Structural Changes of Layer-Structured Cathode for Lithium-Ion Batteries journal August 2016
New Insight into Ni-Rich Layered Structure for Next-Generation Li Rechargeable Batteries journal October 2017
Porous-electrode theory with battery applications journal January 1975
Bayesian Model Selection and Model Averaging journal March 2000
Traité elémentaire de mécanique chimique pondée sur la thermodinamique journal July 1899
Hysteresis and phase transition in many-particle storage systems journal January 2011
Stochastic many-particle model for LFP electrodes journal February 2018
In situ x-ray diffraction and electrochemical studies of Li1−xNiO2 journal December 1993
A comparative study on structural changes of LiCo1/3Ni1/3Mn1/3O2 and LiNi0.8Co0.15Al0.05O2 during first charge using in situ XRD journal August 2006
Phase Transformation Dynamics in Porous Battery Electrodes journal November 2014
Thermal runaway caused fire and explosion of lithium ion battery journal June 2012
First-cycle defect evolution of Li1−xNi1/3Mn1/3Co1/3O2 lithium ion battery electrodes investigated by positron annihilation spectroscopy journal December 2016
The behavior of a many-particle electrode in a lithium-ion battery journal June 2011
Reaction Heterogeneity in LiNi 0.8 Co 0.15 Al 0.05 O 2 Induced by Surface Layer journal August 2017
Evolution of Structure and Lithium Dynamics in LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) Cathodes during Electrochemical Cycling journal March 2019
Charge-Transfer-Induced Lattice Collapse in Ni-Rich NCM Cathode Materials during Delithiation journal October 2017
Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics journal June 2012
X-ray/Neutron Diffraction and Electrochemical Studies of Lithium De/Re-Intercalation in Li 1 - x Co 1/ 3 Ni 1/3 Mn 1/3 O 2 ( x = 0 → 1) journal April 2006
Activation Mechanism of LiNi 0.80 Co 0.15 Al 0.05 O 2 : Surface and Bulk Operando Electrochemical, Differential Electrochemical Mass Spectrometry, and X-ray Diffraction Analyses journal January 2015
Intrinsic Kinetic Limitations in Substituted Lithium-Layered Transition-Metal Oxide Electrodes journal March 2020
Rate-Induced Solubility and Suppression of the First-Order Phase Transition in Olivine LiFePO 4 journal April 2014
The thermodynamic origin of hysteresis in insertion batteries journal April 2010
Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes journal September 2014
Thermodynamic stability of driven open systems and control of phase separation by electro-autocatalysis journal January 2017
Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries journal January 2018
A scaling law to determine phase morphologies during ion intercalation journal January 2020
Phase transition kinetics of LiNi0.5Mn1.5O4 electrodes studied by in situ X-ray absorption near-edge structure and X-ray diffraction analysis journal January 2013
Population dynamics of driven autocatalytic reactive mixtures journal July 2019
Chemical freezing of phase separation in immiscible binary mixtures journal September 1997
Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes journal June 2014
Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles journal August 2016
Kinetic pathways of ionic transport in fast-charging lithium titanate journal February 2020
Electrochemically Driven Phase Transitions in Insertion Electrodes for Lithium-Ion Batteries: Examples in Lithium Metal Phosphate Olivines journal June 2010
Role of Chemical and Structural Stabilities on the Electrochemical Properties of Layered LiNi[sub 1∕3]Mn[sub 1∕3]Co[sub 1∕3]O[sub 2] Cathodes journal January 2005
Contribution of the Structural Changes of LiNi[sub 0.8]Co[sub 0.15]Al[sub 0.05]O[sub 2] Cathodes on the Exothermic Reactions in Li-Ion Cells journal January 2006
Multiphase Porous Electrode Theory journal January 2017
Operando X-ray Diffraction Study of Polycrystalline and Single-Crystal Li x Ni 0.5 Mn 0.3 Co 0.2 O 2 journal January 2017
Study of the Failure Mechanisms of LiNi 0.8 Mn 0.1 Co 0.1 O 2 Cathode Material for Lithium Ion Batteries journal January 2015

Similar Records

Related Subjects

36 MATERIALS SCIENCE