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Title: Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides

Authors:
 [1];  [2];  [1];  [2]
  1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02141, United States
  2. Department of Materials Science and Engineering, UC Berkeley, Berkeley, California 94720, United States; Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388768
DOE Contract Number:
SC0001294
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 28; Journal Issue: 15; 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
Subject:
energy storage (including batteries and capacitors), defects, charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Abdellahi, Aziz, Urban, Alexander, Dacek, Stephen, and Ceder, Gerbrand. Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides. United States: N. p., 2016. Web. doi:10.1021/acs.chemmater.6b01438.
Abdellahi, Aziz, Urban, Alexander, Dacek, Stephen, & Ceder, Gerbrand. Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides. United States. doi:10.1021/acs.chemmater.6b01438.
Abdellahi, Aziz, Urban, Alexander, Dacek, Stephen, and Ceder, Gerbrand. 2016. "Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides". United States. doi:10.1021/acs.chemmater.6b01438.
@article{osti_1388768,
title = {Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides},
author = {Abdellahi, Aziz and Urban, Alexander and Dacek, Stephen and Ceder, Gerbrand},
abstractNote = {},
doi = {10.1021/acs.chemmater.6b01438},
journal = {Chemistry of Materials},
number = 15,
volume = 28,
place = {United States},
year = 2016,
month = 7
}
  • Cation disorder is a phenomenon that is becoming increasingly important for the design of high-energy lithium transition metal oxide cathodes (LiMO 2) for Li-ion batteries. Disordered Li-excess rocksalts have recently been shown to achieve high reversible capacity, while in operando cation disorder has been observed in a large class of ordered compounds. The voltage slope (dV/dx u )is a critical quantity for the design of cation-disordered rocksalts, as it controls the Li capacity accessible at voltages below the stability limit of the electrolyte (~4.5-4.7 V). In this study, we develop a lattice model based on first principles to understand andmore » quantify the voltage slope of cation-disordered LiMO 2. We show that cation disorder increases the voltage slope of Li transition metal oxides by creating a statistical distribution of transition metal environments around Li sites, as well as by allowing Li occupation of highvoltage tetrahedral sites. We further demonstrate that the voltage slope increase upon disorder is generally smaller for highvoltage transition metals than for low-voltage transition metals due to a more effective screening of Li-M interactions by oxygen electrons. Short-range order in practical disordered compounds is found to further mitigate the voltage slope increase upon disorder. In conclusion, our analysis shows that the additional high-voltage tetrahedral capacity induced by disorder is smaller in Liexcess compounds than in stoichiometric LiMO 2 compounds.« less
  • Cation disorder is a phenomenon that is becoming increasingly important for the design of high-energy lithium transition metal oxide cathodes (LiMO 2) for Li-ion batteries. Disordered Li-excess rocksalts have recently been shown to achieve high reversible capacity, while in operando cation disorder has been observed in a large class of ordered compounds. The voltage slope (dV/dx u )is a critical quantity for the design of cation-disordered rocksalts, as it controls the Li capacity accessible at voltages below the stability limit of the electrolyte (~4.5-4.7 V). In this study, we develop a lattice model based on first principles to understand andmore » quantify the voltage slope of cation-disordered LiMO 2. We show that cation disorder increases the voltage slope of Li transition metal oxides by creating a statistical distribution of transition metal environments around Li sites, as well as by allowing Li occupation of highvoltage tetrahedral sites. We further demonstrate that the voltage slope increase upon disorder is generally smaller for highvoltage transition metals than for low-voltage transition metals due to a more effective screening of Li-M interactions by oxygen electrons. Short-range order in practical disordered compounds is found to further mitigate the voltage slope increase upon disorder. In conclusion, our analysis shows that the additional high-voltage tetrahedral capacity induced by disorder is smaller in Liexcess compounds than in stoichiometric LiMO 2 compounds.« less
  • Lithium- and manganese-rich (LMR) transition metal oxide cathodes are of interest for lithium-ion battery applications due to their increased energy density and decreased cost. However, the advantages in energy density and cost are offset, in part, due to the phenomena of voltage fade. Specifically, the voltage profiles (voltage as a function of capacity) of LMR cathodes transform from a high energy configuration to a lower energy configuration as they are repeatedly charged (Li removed) and discharged (Li inserted). Here, we propose a physical model of voltage fade that accounts for the emergence of a low voltage Li phase due tomore » the introduction of transition metal ion defects within a parent Li phase. The phenomenological model was re-cast in a general form and experimental LMR charge profiles were de-convoluted to extract the evolutionary behavior of various components of LMR capacitance profiles. Evolution of the voltage fade component was found to follow a universal growth curve with a maximal voltage fade capacity of ≈ 20% of the initial total capacity.« less