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Title: Effect of composition on the structure of lithium- and manganese-rich transition metal oxides

Abstract

In this work, we establish a definitive structural model for lithium- and manganese-rich transition metal oxides and demonstrate the effect of composition on their bulk as well as the surface structure.

Authors:
ORCiD logo [1];  [2];  [3];  [2];  [2];  [4];  [5];  [5];  [5]
  1. Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, USA, SuperSTEM
  2. SuperSTEM, Daresbury, UK
  3. National Center for Electron Microscopy, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, USA
  4. Erich Schmid Institute of Materials Science, Austrian Academy of Sciences, Leoben, Austria
  5. Envia Systems, Newark, USA
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1420189
Grant/Contract Number:
EE0006443; AC02-05CH11231
Resource Type:
Journal Article: Published Article
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Related Information: CHORUS Timestamp: 2018-02-12 06:06:48; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Shukla, Alpesh Khushalchand, Ramasse, Quentin M., Ophus, Colin, Kepaptsoglou, Despoina Maria, Hage, Fredrik S., Gammer, Christoph, Bowling, Charles, Gallegos, Pedro Alejandro Hernández, and Venkatachalam, Subramanian. Effect of composition on the structure of lithium- and manganese-rich transition metal oxides. United Kingdom: N. p., 2018. Web. doi:10.1039/C7EE02443F.
Shukla, Alpesh Khushalchand, Ramasse, Quentin M., Ophus, Colin, Kepaptsoglou, Despoina Maria, Hage, Fredrik S., Gammer, Christoph, Bowling, Charles, Gallegos, Pedro Alejandro Hernández, & Venkatachalam, Subramanian. Effect of composition on the structure of lithium- and manganese-rich transition metal oxides. United Kingdom. doi:10.1039/C7EE02443F.
Shukla, Alpesh Khushalchand, Ramasse, Quentin M., Ophus, Colin, Kepaptsoglou, Despoina Maria, Hage, Fredrik S., Gammer, Christoph, Bowling, Charles, Gallegos, Pedro Alejandro Hernández, and Venkatachalam, Subramanian. 2018. "Effect of composition on the structure of lithium- and manganese-rich transition metal oxides". United Kingdom. doi:10.1039/C7EE02443F.
@article{osti_1420189,
title = {Effect of composition on the structure of lithium- and manganese-rich transition metal oxides},
author = {Shukla, Alpesh Khushalchand and Ramasse, Quentin M. and Ophus, Colin and Kepaptsoglou, Despoina Maria and Hage, Fredrik S. and Gammer, Christoph and Bowling, Charles and Gallegos, Pedro Alejandro Hernández and Venkatachalam, Subramanian},
abstractNote = {In this work, we establish a definitive structural model for lithium- and manganese-rich transition metal oxides and demonstrate the effect of composition on their bulk as well as the surface structure.},
doi = {10.1039/C7EE02443F},
journal = {Energy & Environmental Science},
number = ,
volume = ,
place = {United Kingdom},
year = 2018,
month = 1
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/C7EE02443F

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  • To evaluate the effect of transition metal composition on the electrochemical properties of Li-rich layer-structured cathode materials, Li{sub 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2, 0.25, 0.3, and 0.4) were synthesized, and their electrochemical properties were investigated. As nickel content x increased in Li{sub 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2, 0.25, 0.3, and 0.4), charge-discharge capacities at a low C-rate (0.05 C) decreased. The results obtained by dQ/dV curves indicate that, as the nickel content increased, the discharge capacity below 3.6 V greatly decreased, but that above 3.6 V increased. As the C-rate of the discharge process increased, the discharge reaction of Li{submore » 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2) below 3.6 V greatly decreased. In contrast, that above 3.6 V slightly decreased. This indicates that the discharge reaction above 3.6 V exhibits higher rate performance than that below 3.6 V. For the high-nickel-content cathodes, the ratio of the discharge capacity above 3.6 V to the total discharge capacity was high. Therefore, they exhibited high rate performance. - Graphical abstract: Figure shows the discharge curves of Li{sub 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2 and 0.3) within potential range of 2.5−4.6 V (vs. Li/Li{sup +}) at 0.05 and 3 C. At low C-rate (0.05 C), the discharge capacity of high-nickel-content cathode (Li{sub 1.2}Ni{sub 0.3}Mn{sub 0.5}O{sub 2}) was less than that of low-nickel-content cathode (Li{sub 1.2}Ni{sub 0.2}Mn{sub 0.6}O{sub 2}); however, the discharge potential and capacity of Li{sub 1.2}Ni{sub 0.3}Mn{sub 0.5}O{sub 2} was higher than those of Li{sub 1.2}Ni{sub 0.2}Mn{sub 0.6}O{sub 2} at high C-rate (3 C). This means that the increase in Ni/Mn ratio was effective in improving rate-performance.« less
  • Although Li- and Mn-rich transition metal oxides have been extensively studied as high-capacity cathode materials for Li-ion batteries, the crystal structure of these materials in their pristine state is not yet fully understood. Here we apply complementary electron microscopy and spectroscopy techniques at multi-length scale on well-formed Li1.2(Ni0.13Mn0.54Co0.13)O2 crystals with two different morphologies as well as two commercially available materials with similar compositions, and unambiguously describe the structural make-up of these samples. Systematically observing the entire primary particles along multiple zone axes reveals that they are consistently made up of a single phase, save for rare localized defects and amore » thin surface layer on certain crystallographic facets. Finally and more specifically, we show the bulk of the oxides can be described as an aperiodic crystal consisting of randomly stacked domains that correspond to three variants of monoclinic structure, while the surface is composed of a Co- and/or Ni-rich spinel with antisite defects.« 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
  • Although Li- and Mn-rich transition metal oxides have been extensively studied as high-capacity cathode materials for Li-ion batteries, the crystal structure of these materials in their pristine state is not yet fully understood. Here we apply complementary electron microscopy and spectroscopy techniques at multi-length scale on well-formed Li 1.2 (Ni 0.13 Mn 0.54 Co 0.13)O 2 crystals with two different morphologies as well as two commercially available materials with similar compositions, and unambiguously describe the structural make-up of these samples. Systematically observing the entire primary particles along multiple zone axes reveals that they are consistently made up of a singlemore » phase, save for rare localized defects and a thin surface layer on certain crystallographic facets. More specifically, we show the bulk of the oxides can be described as an aperiodic crystal consisting of randomly stacked domains that correspond to three variants of monoclinic structure, while the surface is composed of a Co- and/or Ni-rich spinel with antisite defects.« less
  • The effect of composition on the voltage fade phenomenon was probed using combinatorial synthesis methods. In compositions that have the general formula, (Li 2MnO 3) a(LiNiO 2) b(LiMnO 2) c(LiCoO 2) d, where 0 ≤ a≤0.83, 0.15 ≤ b ≤ 0.42, 0 ≤ c ≤ 0.85, and 0 ≤ d ≤ 0.30 (a + b + c + d = 1), the dependence of features in the x-ray diffraction pattern and of voltage fade on composition were identified and mapped. The observed values of voltage fade indicated that it displayed some sensitivity to composition, but that the sensitivity was notmore » large. The values of voltage fade were found to be amenable to statistical modeling. The model indicated that it may be possible to lower the value of voltage fade below 0.01% by adjusting the composition of the system; however, the composition is not expected to have the layered–layered structure.« less