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Title: Quaternary phase diagrams of spinel Liy$$\square$$ 1-yMn xNi 2-xO 4 and composite cathode voltages for concentration gradient materials

Abstract

$$\square$$

Authors:
; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388323
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review B; Journal Volume: 94; Journal Issue: 1; Related Information: CEES partners with Argonne National Laboratory (lead); University of Illinois, Urbana-Champaign; Northwest University
Country of Publication:
United States
Language:
English
Subject:
energy storage (including batteries and capacitors), charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Hao, Shiqiang, Lu, Zhi, and Wolverton, Christopher. Quaternary phase diagrams of spinel Liy$\square$1-yMnxNi2-xO4 and composite cathode voltages for concentration gradient materials. United States: N. p., 2016. Web. doi:10.1103/PhysRevB.94.014114.
Hao, Shiqiang, Lu, Zhi, & Wolverton, Christopher. Quaternary phase diagrams of spinel Liy$\square$1-yMnxNi2-xO4 and composite cathode voltages for concentration gradient materials. United States. doi:10.1103/PhysRevB.94.014114.
Hao, Shiqiang, Lu, Zhi, and Wolverton, Christopher. 2016. "Quaternary phase diagrams of spinel Liy$\square$1-yMnxNi2-xO4 and composite cathode voltages for concentration gradient materials". United States. doi:10.1103/PhysRevB.94.014114.
@article{osti_1388323,
title = {Quaternary phase diagrams of spinel Liy$\square$1-yMnxNi2-xO4 and composite cathode voltages for concentration gradient materials},
author = {Hao, Shiqiang and Lu, Zhi and Wolverton, Christopher},
abstractNote = {$\square$},
doi = {10.1103/PhysRevB.94.014114},
journal = {Physical Review B},
number = 1,
volume = 94,
place = {United States},
year = 2016,
month = 7
}
  • Pristine Li-rich layered cathodes, such as Li1.2Ni0.2Mn0.6O2 and Li1.2Ni0.1Mn0.525Co0.175O2, were identified to exist in two different structures: LiMO2 R-3m and Li2MO3 C2/m phases. Upon charge/discharge cycling, both phases gradually transform to the spinel structure. The transition from LiMO2 R-3m to spinel is accomplished through the migration of transition metal ions to the Li site without breaking down the lattice, leading to the formation of mosaic structured spinel grains within the parent particle. In contrast, transition from Li2MO3 C2/m to spinel involves removal of Li+ and O2-, which produces a large lattice strain and leads to the breakdown of the parentmore » lattice and therefore the newly formed spinel grains show random orientation within the same particle. Cracks and pores were also noticed within some particles, which is believed to be the consequence of the breakdown of the lattice and vacancy condensation upon removal of lithium ions. The presently observed structure transition characteristics provide direct reasons for the observed gradual capacity loss and poor rate performance of the layered composite. Ultimately it also provides clues about how to improve the materials structure with potential improved performance.« less
  • LiMn{sub 2}O{sub 4}-based spinels are of great interest as positive electrode materials for lithium-ion batteries. The authors describe here what is believed to be the first synthesis of these materials using the Pechini process, a low temperature synthetic method that often yields inorganic oxides of excellent phase purity and well-controlled stoichiometry. Using this process, it has been possible to synthesize phase-pure crystalline spinel LiMn{sub 2}O{sub 4} by calcining the appropriate polymeric precursors in air at 250 C for several hours. The influence of different firing temperatures and the effect of substituting a small amount of Mn with Ni have alsomore » been explored. Electrochemical studies show that the Pechini-synthesized materials appear to offer not only high quality performance but also significant analytical advantages which allows one to understand the structural mechanism of Li intercalation.« less
  • In the past ten years, LiMn{sub 2}O{sub 4}-based spinels have been extensively studied as positive electrode materials for lithium-ion batteries. Ongoing investigations have shown that the Pechini process, a low temperature synthetic method that often yields inorganic oxides of excellent phase purity and well-controlled stoichiometry, is very effective for preparing LiMn{sub 2}O{sub 4}-based cathode materials. It also has been shown that different firing temperatures and the selective doping of LiMn{sub 2}O{sub 4} both produce materials with different electrochemical characteristics that merit further exploration.
  • A series of spinel-structured materials have been prepared by a simple hydrothermal procedure in an aqueous medium. The new synthetic method is time and energy saving i.e., no further thermal treatment and extended grinding. The main experimental process involved the insertion of lithium into electrolytic manganese dioxide with glucose as a mild reductant in an autoclave. Both the hydrothermal temperature and the presence of glucose play the critical roles in determining the final spinel integrity. Particular electrochemical performance has also been systematically explored, and the results show that Al{sup 3+}, F{sup -} co-substituted spinels have the best combination of initialmore » capacity and capacity retention among all these samples, exhibited the initial capacity of 115 mAh/g and maintained more than 90% of the initial value at the 50th cycle. - Graphical abstract: It is a SEM image of the spinel LiMn{sub 2}O{sub 4}, which was prepared by this novel hydrothermal procedure. It illustrates that reasonable-crystallized spinel oxide has occurred through the special hydrothermal process and the average particle size declined to about 1 {mu}m. This homogeneous grain size distribution provides an important morphological basis for the reversibility and accessibility of lithium ion insertion/extraction reactions.« less