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Title: High voltage cathode compositions for lithium-ion batteries

Abstract

A lithium transition metal oxide composition. The composition has the formula Li.sub.a[Li.sub.bNi.sub.cMn.sub.dCo.sub.e]O.sub.2, where a.gtoreq.0.9, b.gtoreq.0, c>0, d>0, e>0, b+c+d+e=1, 1.05.ltoreq.c/d.ltoreq.1.4, 0.05.ltoreq.e.ltoreq.0.30, 0.9.ltoreq.(a+b)/M.ltoreq.1.06, and M=c+d+e. The composition has an O3 type structure.

Inventors:
;
Publication Date:
Research Org.:
3M INNOVATIVE PROPERTIES COMPANY, St. Paul, MN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1347540
Patent Number(s):
9,601,771
Application Number:
15/223,786
Assignee:
3M INNOVATIVE PROPERTIES COMPANY DOEEE
DOE Contract Number:
EE0005499
Resource Type:
Patent
Resource Relation:
Patent File Date: 2016 Jul 29
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE

Citation Formats

Lu, Zhonghua, and Eberman, Kevin W. High voltage cathode compositions for lithium-ion batteries. United States: N. p., 2017. Web.
Lu, Zhonghua, & Eberman, Kevin W. High voltage cathode compositions for lithium-ion batteries. United States.
Lu, Zhonghua, and Eberman, Kevin W. Tue . "High voltage cathode compositions for lithium-ion batteries". United States. doi:. https://www.osti.gov/servlets/purl/1347540.
@article{osti_1347540,
title = {High voltage cathode compositions for lithium-ion batteries},
author = {Lu, Zhonghua and Eberman, Kevin W},
abstractNote = {A lithium transition metal oxide composition. The composition has the formula Li.sub.a[Li.sub.bNi.sub.cMn.sub.dCo.sub.e]O.sub.2, where a.gtoreq.0.9, b.gtoreq.0, c>0, d>0, e>0, b+c+d+e=1, 1.05.ltoreq.c/d.ltoreq.1.4, 0.05.ltoreq.e.ltoreq.0.30, 0.9.ltoreq.(a+b)/M.ltoreq.1.06, and M=c+d+e. The composition has an O3 type structure.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Mar 21 00:00:00 EDT 2017},
month = {Tue Mar 21 00:00:00 EDT 2017}
}

Patent:

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  • Lithium ion batteries (LIBs) are attracting intensive interests worldwide because of their potential applications in transportation electrification and utility grid. The intercalation compounds used in LIBs electrochemically react with Li+ ions via single or multiple phase transitions depending on the nature of the material structure as well as the synthesis and testing conditions. It is generally accepted that for high voltage spinel LiNi0.5Mn1.5O4, a promising candidate for LIBs, there are two successive two-phase reactions occurring during the delithiation/lithiation processes, as reflected by the two flat plateaus with a small step in between. Here we demonstrate, experimentally and theoretically, that throughmore » elemental substitution, each of the two-phase transitions has been largely converted into a solid solution reaction during the electrochemical process. The latter favors fast Li+ diffusion due to the reduced number of phase boundaries that Li+ ions have to overcome, as well as the reduced shrinkage of unit cells after charge. This work clearly elaborates one of the critical functions for element doping/substitution that has been widely adopted in the materials synthesis for LIBs, whose fundamental mechanisms are still obscured.« less
  • A new mechanistic framework is suggested to account for the protective action of certain electrolyte additives on high-voltage positive electrode (cathode) materials. The mechanism involves inactivation of catalytically active centers on the electrode active materials through fragmentation reactions involving molecules at its surface. The cathode protection additives oxidize before the solvent and serve as sacrificial inhibitors of the catalytic centers. Without the additive, the surface oxidation of the solvent (like solvent oxidation in the bulk) yields H loss radicals and releases the proton that can combine with anions forming corrosive acids. This proton-release reaction is demonstrated experimentally for boronate additives.more » Specific radical reactions for the latter additives on the electrode surface are suggested. Furthermore, the same approach can be used to rationalize the protective action of other additives and account for various observations regarding their performance.« less
  • LiNi 1/3Mn 1/3Co 1/3O 2 (NMC333) layered cathode is often fabricated as secondary particles of consisting of densely packed primary particles, which offers advantage of high energy density and alleviation of cathode side reactions/corrosions, but introduces other drawbacks, such as intergranular cracking. Here, we report unexpected observations on the nucleation and growth of intragranular cracks in the commercial NMC333 layered cathode by using advanced S/TEM. We found that the formation of the intragranular cracks is directly associated with high voltage cycling, which is an electrochemically driven and diffusion controlled process. The intragranular cracks were noticed to be characteristically initiated frommore » grain interior, a consequence of dislocation based crack incubation mechanism. This observation is in sharp contrast with the general theoretical models, predicting the initiation of intragranular cracks from grain boundaries or particle surface. As a result, our study indicates that maintain a structural stability is the key step toward high voltage operation of layered cathode materials.« less