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Title: A new anion receptor for improving the interface between lithium- and manganese-rich layered oxide cathode and the electrolyte

Abstract

Surface degradation on cycled lithium-ion battery cathode particles is governed not only by intrinsic thermodynamic properties of the material but also, oftentimes more predominantly, by the side reactions with the electrolytic solution. A superior electrolyte inhibits these undesired side reactions on the cathode and at the electrolyte interface, which consequently minimizes the deterioration of the cathode surface. The present study investigates a new boron-based anion receptor, tris(2,2,2-trifluoroethyl)borate (TTFEB), as an electrolyte additive in cells containing a lithium- and manganese-rich layered oxide cathode, Li 1.16Ni 0.2Co 0.1Mn 0.54O 2. Our electrochemical studies demonstrate that the cycling performance and Coulombic efficiency are significantly improved because of the additive, in particular, under elevated temperature conditions. Spectroscopic analyses revealed that the addition of 0.5 wt % TTFEB is capable of reducing the content of lithium-containing inorganic species within the cathode-electrolyte interphase layer and minimizing the reduction of tetravalent Mn4+ at the cathode surface. Furthermore, our work introduces a novel additive highly effective in improving lithium-ion battery performance, highlights the importance in preserving the surface properties of cathode materials, and provides new insights on the working mechanism of electrolyte additives.

Authors:
 [1];  [2];  [2];  [2];  [2];  [3];  [4];  [2]; ORCiD logo [2];  [3];  [5]; ORCiD logo [6]; ORCiD logo [5]
  1. Harbin Institute of Technology, Harbin (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Harbin Institute of Technology, Harbin (China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1360187
Grant/Contract Number:
AC02-76SF00515; AC02-05CH11231; 21373072; 51202047; LBH-Z11141
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 5; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE

Citation Formats

Ma, Yulin, Zhou, Yan, Du, Chunyu, Zuo, Pengjian, Cheng, Xinqun, Han, Lili, Nordlund, Dennis, Gao, Yunzhi, Yin, Geping, Xin, Huolin L., Doeff, Marca M., Lin, Feng, and Chen, Guoying. A new anion receptor for improving the interface between lithium- and manganese-rich layered oxide cathode and the electrolyte. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.6b04784.
Ma, Yulin, Zhou, Yan, Du, Chunyu, Zuo, Pengjian, Cheng, Xinqun, Han, Lili, Nordlund, Dennis, Gao, Yunzhi, Yin, Geping, Xin, Huolin L., Doeff, Marca M., Lin, Feng, & Chen, Guoying. A new anion receptor for improving the interface between lithium- and manganese-rich layered oxide cathode and the electrolyte. United States. doi:10.1021/acs.chemmater.6b04784.
Ma, Yulin, Zhou, Yan, Du, Chunyu, Zuo, Pengjian, Cheng, Xinqun, Han, Lili, Nordlund, Dennis, Gao, Yunzhi, Yin, Geping, Xin, Huolin L., Doeff, Marca M., Lin, Feng, and Chen, Guoying. Wed . "A new anion receptor for improving the interface between lithium- and manganese-rich layered oxide cathode and the electrolyte". United States. doi:10.1021/acs.chemmater.6b04784. https://www.osti.gov/servlets/purl/1360187.
@article{osti_1360187,
title = {A new anion receptor for improving the interface between lithium- and manganese-rich layered oxide cathode and the electrolyte},
author = {Ma, Yulin and Zhou, Yan and Du, Chunyu and Zuo, Pengjian and Cheng, Xinqun and Han, Lili and Nordlund, Dennis and Gao, Yunzhi and Yin, Geping and Xin, Huolin L. and Doeff, Marca M. and Lin, Feng and Chen, Guoying},
abstractNote = {Surface degradation on cycled lithium-ion battery cathode particles is governed not only by intrinsic thermodynamic properties of the material but also, oftentimes more predominantly, by the side reactions with the electrolytic solution. A superior electrolyte inhibits these undesired side reactions on the cathode and at the electrolyte interface, which consequently minimizes the deterioration of the cathode surface. The present study investigates a new boron-based anion receptor, tris(2,2,2-trifluoroethyl)borate (TTFEB), as an electrolyte additive in cells containing a lithium- and manganese-rich layered oxide cathode, Li1.16Ni0.2Co0.1Mn0.54O2. Our electrochemical studies demonstrate that the cycling performance and Coulombic efficiency are significantly improved because of the additive, in particular, under elevated temperature conditions. Spectroscopic analyses revealed that the addition of 0.5 wt % TTFEB is capable of reducing the content of lithium-containing inorganic species within the cathode-electrolyte interphase layer and minimizing the reduction of tetravalent Mn4+ at the cathode surface. Furthermore, our work introduces a novel additive highly effective in improving lithium-ion battery performance, highlights the importance in preserving the surface properties of cathode materials, and provides new insights on the working mechanism of electrolyte additives.},
doi = {10.1021/acs.chemmater.6b04784},
journal = {Chemistry of Materials},
number = 5,
volume = 29,
place = {United States},
year = {Wed Feb 15 00:00:00 EST 2017},
month = {Wed Feb 15 00:00:00 EST 2017}
}

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  • We find that the electrochemical rate performance and capacity retention of the “layered–layered” lithium rich Li 1.2Mn 0.525Ni 0.175Co 0.1O 2(Li-rich NMC) material are significantly improved by a nanometer layer coating of a lithium conducting solid electrolyte, lithium phosphorus oxynitride (LiPON). The LiPON layer is deposited on the Li-rich NMC particles by the RF-magnetron sputtering method. The presence of the LiPON layer provides interfacial stability under high current (rate) and voltage cycling conditions and thereby improves the capacity retention over cycle life compared to pristine or uncoated Li-rich NMC. Specifically, the LiPON coated Li-rich NMC composite electrode showed stable reversiblemore » capacities of >275 mAh g -1 when cycled to 4.9 V for more than 300 cycles, and showed at least threefold improvements in the rate performance compared to the uncoated electrode compositions. Increasing the LiPON layer thickness beyond a few nanometers leads to capacity fade due to increasing electronic resistance. Lastly, detailed microstructural and electrochemical impedance spectroscopy studies are undertaken to characterize and understand the role of LiPON in improving the interfacial stability and electrochemical activity at the interface.« less
  • Structure–electrochemical property correlation is presented for lithium–manganese-rich layered–layered nickel manganese cobalt oxide (LMR–NMC) having composition Li1.2Co0.1Mn0.55Ni0.15O2 (TODA HE5050) in order to examine the possible reasons for voltage fade during short-to-mid-term electrochemical cycling. The Li1.2Co0.1Mn0.55Ni0.15O2 based cathodes were cycled at two different upper cutoff voltages (UCV), 4.2 V and 4.8 V, for 1, 10, and 125 cycles; voltage fade was observed after 10 and 125 cycles only when the UCV was 4.8 V. Magnetic susceptibility and selected-area electron diffraction data showed the presence of cation ordering in the pristine material, which remained after 125 cycles when the UCV was 4.2 V.more » When cycled at 4.8 V, the magnetic susceptibility results showed the suppression of cation ordering after one cycle; the cation ordering diminished upon further cycling and was not observed after 125 cycles. Selected-area electron diffraction data from oxides oriented towards the [0001] zone axis revealed a decrease in the intensity of cation-ordering reflections after one cycle and an introduction of spinel-type reflections after 10 cycles at 4.8 V; after 125 cycles, only the spinel-type reflections and the fundamental O3 layered oxide reflections were observed. A significant decrease in the effective magnetic moment of the compound after one cycle at 4.8 V indicated the presence of lithium and/or oxygen vacancies; analysis showed a reduction of Mn4+ (high spin/low spin) in the pristine oxide to Mn3+ (low spin) after one cycle. The effective magnetic moment was higher after 10 and 125 cycles at 4.8 V, suggesting the presence of Mn3+ in a high spin state, which is believed to originate from distorted spinel (Li2Mn2O4) and/or spinel (LiMn2O4) compounds. The increase in effective magnetic moments was not observed when the oxide was cycled at 4.2 V, indicating the stability of the structure under these conditions. This study shows that structural rearrangements in the LMR–NMC oxide happen only at higher potentials (4.8 V, for example) and provides evidence of a direct correlation between cation ordering and voltage fade.« less
  • No abstract prepared.