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

Title: Unveiling the parasitic-reaction-driven surface reconstruction in Ni-rich cathode and the electrochemical role of Li2CO3

Journal Article · · Journal of Energy Chemistry
ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [2];  [2]; ORCiD logo [1];  [1];  [3];  [3];  [3];  [4];  [4]; ORCiD logo [5];  [6];  [6]; ORCiD logo [6];  [6];  [7];  [1] more »;  [1] « less
  1. Argonne National Laboratory (ANL), Argonne, IL (United States)
  2. Brookhaven National Laboratory (BNL), Upton, NY (United States)
  3. Beijing Easprint Material Technology Co. Ltd. (China)
  4. Tsinghua Univ., Beijing (China)
  5. Univ. of Arkansas, Fayetteville, AR (United States)
  6. Binghamton Univ., NY (United States)
  7. Primet Precision Materials, Ithaca, NY (United States)
+ Show Author Affiliations

Nickel-rich transition-metal oxides are widely regarded as promising cathode materials for high-energy-density lithium-ion batteries for emerging electric vehicles. However, achieving high energy density in Ni-rich cathodes is accompanied by substantial safety and cycle-life obstacles. The major issues of Ni-rich cathodes at high working potentials are originated from the unstable cathode-electrolyte interface, while the underlying mechanism of parasitic reactions towards surface reconstructions of cathode materials is not well understood. In this work, we controlled the Li2CO3 impurity content on LiNi0.83Mn0.1Co0.07O2 cathodes using air, tank-air, and O2 synthesis environments. Home-built high-precision leakage current and on-line electrochemical mass spectroscopy experiments verify that Li2CO3 impurity is a significant promoter of parasitic reactions on Ni-rich cathodes. The rate of parasitic reactions is strongly correlated to Li2CO3 content and severe performance deterioration of Ni83 cathodes. The post-mortem characterizations via high-resolution transition electron microscope and X-ray photoelectron spectroscopy depth profiles reveal that parasitic reactions promote more Ni reduction and O deficiency and even rock-salt phase transformation at the surface of cathode materials. Here, our observation suggests that surface reconstructions have a strong affiliation to parasitic reactions that create chemically acidic environment to etch away the lattice oxygen and offer the electrical charge to reduce the valence state of transition metal. Thus, this study advances our understanding on surface reconstructions of Ni-rich cathodes and prepares us for searching for rational strategies.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO)
Grant/Contract Number:
SC0012704; AC02-06CH11357
OSTI ID:
2319173
Report Number(s):
BNL-225362-2024-JAAM
Journal Information:
Journal of Energy Chemistry, Vol. 85; ISSN 2095-4956
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (42)

Observation of Microstructural Evolution in Li Battery Cathode Oxide Particles by In Situ Electron Microscopy journal May 2013
Nickel-Rich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries journal March 2015
Effects of long-term fast charging on a layered cathode for lithium-ion batteries journal April 2022
An effective method to reduce residual lithium compounds on Ni-rich Li[Ni0.6Co0.2Mn0.2]O2 active material using a phosphoric acid derived Li3PO4 nanolayer journal December 2014
Factors Influencing the Layered to Spinel-like Phase Transition in Layered Oxide Cathodes journal January 2002
Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries journal February 2017
Performance and cost of materials for lithium-based rechargeable automotive batteries journal April 2018
A Review of Degradation Mechanisms and Recent Achievements for Ni‐Rich Cathode‐Based Li‐Ion Batteries journal November 2021
Development of Microstrain in Aged Lithium Transition Metal Oxides journal June 2014
Surface Modification for Suppressing Interfacial Parasitic Reactions of a Nickel-Rich Lithium-Ion Cathode journal March 2019
Li2CO3 in LiNi0.8Co0.15Al0.05O2 cathodes and its effects on capacity and power journal August 2004
Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells journal December 2016
Oxidative Stability and Initial Decomposition Reactions of Carbonate, Sulfone, and Alkyl Phosphate-Based Electrolytes journal April 2013
Identifying Active Sites for Parasitic Reactions at the Cathode–Electrolyte Interface journal January 2019
An Unavoidable Challenge for Ni-Rich Positive Electrode Materials for Lithium-Ion Batteries journal August 2019
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries journal March 2014
Additive engineering for robust interphases to stabilize high-Ni layered structures at ultra-high voltage of 4.8 V journal May 2022
Origin of Carbon Dioxide Evolved during Cycling of Nickel-Rich Layered NCM Cathodes journal October 2018
Effect of Residual Lithium Compounds on Layer Ni-Rich Li[Ni 0.7 Mn 0.3 ]O 2 journal January 2014
Li2CO3 decomposition in Li-ion batteries induced by the electrochemical oxidation of the electrolyte and of electrolyte impurities journal June 2020
Tuning charge–discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries journal November 2014
Ultra High-Precision Studies of Degradation Mechanisms in Aged LiCoO 2 /Graphite Li-Ion Cells journal January 2014
Kinetic Study of Parasitic Reactions in Lithium-Ion Batteries: A Case Study on LiNi 0.6 Mn 0.2 Co 0.2 O 2 journal January 2016
Quantification of Surface Oxygen Depletion and Solid Carbonate Evolution on the First Cycle of LiNi 0.6 Mn 0.2 Co 0.2 O 2 Electrodes journal April 2019
Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries journal January 2017
Controllable Cathode–Electrolyte Interface of Li[Ni 0.8 Co 0.1 Mn 0.1 ]O 2 for Lithium Ion Batteries: A Review journal August 2019
Phase Transformation Behavior and Stability of LiNiO 2 Cathode Material for Li‐Ion Batteries Obtained from In Situ Gas Analysis and Operando X‐Ray Diffraction journal April 2019
Washing Effect of a LiNi[sub 0.83]Co[sub 0.15]Al[sub 0.02]O[sub 2] Cathode in Water journal January 2006
Transition metal dissolution and deposition in Li-ion batteries investigated by operando X-ray absorption spectroscopy journal January 2016
Stability of Li 2 CO 3 in cathode of lithium ion battery and its influence on electrochemical performance journal January 2016
Surface degradation of Li1–xNi0.80Co0.15Al0.05O2 cathodes: Correlating charge transfer impedance with surface phase transformations journal June 2016
Unveiling the Role of Al 2 O 3 in Preventing Surface Reconstruction During High-Voltage Cycling of Lithium-Ion Batteries journal January 2019
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries journal October 2004
Residual Lithium Carbonate Predominantly Accounts for First Cycle CO 2 and CO Outgassing of Li-Stoichiometric and Li-Rich Layered Transition-Metal Oxides journal November 2017
Understanding Transition-Metal Dissolution Behavior in LiNi 0.5 Mn 1.5 O 4 High-Voltage Spinel for Lithium Ion Batteries journal July 2013
Collapse of LiNi 1– x – y Co x Mn y O 2 Lattice at Deep Charge Irrespective of Nickel Content in Lithium-Ion Batteries journal March 2019
High-voltage positive electrode materials for lithium-ion batteries journal January 2017
Capacity Fading of Ni-Rich Li[Ni x Co y Mn 1– x – y ]O 2 (0.6 ≤ x ≤ 0.95) Cathodes for High-Energy-Density Lithium-Ion Batteries: Bulk or Surface Degradation? journal January 2018
Nickel, Manganese, and Cobalt Dissolution from Ni-Rich NMC and Their Effects on NMC622-Graphite Cells journal January 2019
Cycling Behavior of NCM523/Graphite Lithium-Ion Cells in the 3–4.4 V Range: Diagnostic Studies of Full Cells and Harvested Electrodes journal September 2016
Degradation Mechanisms and Mitigation Strategies of Nickel-Rich NMC-Based Lithium-Ion Batteries journal October 2019
Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries journal December 2012

Similar Records

Electrolyte Reactivity at the Charged Ni-Rich Cathode Interface and Degradation in Li-Ion Batteries
Journal Article · Tue Mar 08 00:00:00 EST 2022 · ACS Applied Materials and Interfaces · OSTI ID:2319173
+7 more
Surface Modification for Suppressing Interfacial Parasitic Reactions of a Nickel-Rich Lithium-Ion Cathode
Journal Article · Fri Mar 29 00:00:00 EDT 2019 · Chemistry of Materials · OSTI ID:2319173
+5 more
Degradation in Ni-Rich LiNi1–x–yMnxCoyO2/Graphite Batteries: Impact of Charge Voltage and Ni Content
Journal Article · Thu Apr 06 00:00:00 EDT 2023 · Journal of Physical Chemistry. C · OSTI ID:2319173
+10 more

Related Subjects

36 MATERIALS SCIENCE
Ni-rich cathodes
Surface reconstructions
Phase transformation
Parasitic reactions
Li2CO3