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Title: Thermal and electrochemical characterization of MCMB/LiNi{sub 1/3}Co{sub l/3}Mn{sub l/3}O{sub 2} using LiBoB as an electrolyte additive.

Abstract

The gas generation associated with the use of the lithium bis(oxalate)borate--(LiBoB) based electrolyte at the elevated temperature were detected in the pouch cell (MCMB/LiNi1/3Co1/3Mn1/3O2 with 10% excess Li), which might prevent the LiBoB usage as a salt. However, the cell capacity retention was improved significantly, from 87 to 96% at elevated temperature, when using LiBoB as an electrolyte additive. The capacity fade during cycling is discussed using dQ/dE, area specific impedance, and frequency response analysis results. Most of the capacity loss in the cell is associated with the rise in the cell impedance. Moreover, results from the differential scanning calorimetry indicate that the thermal stability of the negative electrode with the solid electrolyte interface (SEI) formed by the reduction of the LiBoB additive was greatly improved compared with that obtained from the reduction of LiPF6-based electrolyte without additive. In this case, the onset temperature of the breakdown of the LiBoB-based SEI is 150 C which is higher than that of the conventional electrolyte without additive. Furthermore, the total heat generated between 60 and 170 C is reduced from 213 to 70 J g{sup -1} when using LiBoB as electrolyte additive compared to the one without additive. In addition, the thermalmore » stability of the charged LiNi1/3Co1/3Mn1/3O2 with 10% excess Li was not affected when using LiBoB as an electrolyte additive.« less

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
EE
OSTI Identifier:
915324
Report Number(s):
ANL/CMT/JA-56593
Journal ID: ISSN 0378-7753; JPSODZ; TRN: US200817%%318
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Power Sources; Journal Volume: 163; Journal Issue: 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; METAL-NONMETAL BATTERIES; LITHIUM COMPOUNDS; BORATES; LITHIUM OXIDES; NICKEL OXIDES; COBALT OXIDES; MANGANESE OXIDES; ADDITIVES; CAPACITY; SOLID ELECTROLYTES

Citation Formats

Lu, W., Chen, Z., Joachin, H., Prakash, J., Liu, J., Amine, K., Chemical Engineering, and Illinois Inst. of Tech.. Thermal and electrochemical characterization of MCMB/LiNi{sub 1/3}Co{sub l/3}Mn{sub l/3}O{sub 2} using LiBoB as an electrolyte additive.. United States: N. p., 2007. Web. doi:10.1016/j.jpowsour.2006.09.010.
Lu, W., Chen, Z., Joachin, H., Prakash, J., Liu, J., Amine, K., Chemical Engineering, & Illinois Inst. of Tech.. Thermal and electrochemical characterization of MCMB/LiNi{sub 1/3}Co{sub l/3}Mn{sub l/3}O{sub 2} using LiBoB as an electrolyte additive.. United States. doi:10.1016/j.jpowsour.2006.09.010.
Lu, W., Chen, Z., Joachin, H., Prakash, J., Liu, J., Amine, K., Chemical Engineering, and Illinois Inst. of Tech.. Mon . "Thermal and electrochemical characterization of MCMB/LiNi{sub 1/3}Co{sub l/3}Mn{sub l/3}O{sub 2} using LiBoB as an electrolyte additive.". United States. doi:10.1016/j.jpowsour.2006.09.010.
@article{osti_915324,
title = {Thermal and electrochemical characterization of MCMB/LiNi{sub 1/3}Co{sub l/3}Mn{sub l/3}O{sub 2} using LiBoB as an electrolyte additive.},
author = {Lu, W. and Chen, Z. and Joachin, H. and Prakash, J. and Liu, J. and Amine, K. and Chemical Engineering and Illinois Inst. of Tech.},
abstractNote = {The gas generation associated with the use of the lithium bis(oxalate)borate--(LiBoB) based electrolyte at the elevated temperature were detected in the pouch cell (MCMB/LiNi1/3Co1/3Mn1/3O2 with 10% excess Li), which might prevent the LiBoB usage as a salt. However, the cell capacity retention was improved significantly, from 87 to 96% at elevated temperature, when using LiBoB as an electrolyte additive. The capacity fade during cycling is discussed using dQ/dE, area specific impedance, and frequency response analysis results. Most of the capacity loss in the cell is associated with the rise in the cell impedance. Moreover, results from the differential scanning calorimetry indicate that the thermal stability of the negative electrode with the solid electrolyte interface (SEI) formed by the reduction of the LiBoB additive was greatly improved compared with that obtained from the reduction of LiPF6-based electrolyte without additive. In this case, the onset temperature of the breakdown of the LiBoB-based SEI is 150 C which is higher than that of the conventional electrolyte without additive. Furthermore, the total heat generated between 60 and 170 C is reduced from 213 to 70 J g{sup -1} when using LiBoB as electrolyte additive compared to the one without additive. In addition, the thermal stability of the charged LiNi1/3Co1/3Mn1/3O2 with 10% excess Li was not affected when using LiBoB as an electrolyte additive.},
doi = {10.1016/j.jpowsour.2006.09.010},
journal = {J. Power Sources},
number = 2007,
volume = 163,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • The electrolyte additive, 3,9-divinyl-2,4,8,10-tetraoxaspiro[5,5] undecane (TOS), was investigated as a means to improve the life of mesocarbon microbead (MCMB)/Li1.1[Ni1/3Co1/3Mn1/3]0.9O2 (NCM) cells for high-power applications. With the addition of an appropriate amount of TOS (no more than 1 wt%) to MCMB/NCM cells, the capacity retention was significantly improved at 55 C compared with cells containing pristine electrolyte. Aging tests at 55 C indicated that the capacity retention of the negative electrode had benefited as a result of the formation of a stable passivation film at the surface of the carbon electrode due to TOS reduction. Electrochemical impedance spectroscopy showed that amore » TOS addition of more than 0.5 wt% increased the cell interfacial impedance. Differential scanning calorimetry showed that the thermal stability of lithiated MCMB was also improved with the TOS addition.« less
  • The effects of glutaric anhydride (GA) as an electrolyte additive for graphite/LiNi0.5Mn0.3Co0.2O2 full cells operating between 3.0-4.4 V were investigated. Linear scan voltammetry (LSV) revealed that GA preferentially oxidized prior to the carbonate-based electrolyte while Li/graphite half cells revealed that GA can suppress electrolyte decomposition on the graphite electrode giving rise to the bifunctional nature of this additive. The addition of both 0.5 and 1.0 wt% of GA into the carbonate-based electrolyte resulted in superior cycling performance compared to the baseline electrolyte as demonstrated by the slight increase in initial capacities and significant increases in capacity retention over 117 cyclesmore » at C/3. Electrochemical impedance spectroscopy (EIS) showed that while the overall impedance of the GA containing cells was higher than the cells with the baseline electrolyte the change in impedance between post-formation and post-cycling was smallest for the cells containing GA. Additionally, X-ray photoelectron spectroscopy (XPS) analysis confirmed that GA decomposed on the cathode surface leading to an increase in oxygen-containing species, a decrease in LiF species and a simultaneous increase in LixPOyFz species. (C) 2016 The Electrochemical Society. All rights reserved.« less
  • The authors report the synthesis and electrochemical properties of highly stoichiometric LiNi{sub 1{minus}z}M{sub z}O{sub 2} (M = Co, Mn, Ti, z {le} 0.3) samples. With the excess lithium method, samples with a well-defined layered structure can be prepared in air. A large rechargeable capacity of about 200 mAh/g is obtained for 10% substitutives. Structural changes during charging and lithium ordering phenomena are discussed. The authors describe the thermal behavior of the substitutives and report the enhanced thermal stability and large rechargeable capacity of the manganese substitutives.
  • Graphical abstract: A low-temperature reaction route is introduced based on hydroxide precipitation method to synthesize a cathode material LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2}. The charge-discharge tests were performed at 1000 mA g{sup -1} between 2.5 and 4.5 V and the discharge capacity is about 160 mAh g{sup -1}. The discharge capacity of the material is strongly impacted by the reaction temperature. The powders sintered at 850 {sup o}C show the best electrochemical performance. Highlights: {yields} A low-temperature reaction route is introduced based on hydroxide precipitation method to synthesize a novel cathode material LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2}. {yields} The charge-dischargemore » tests were performed at higher current as 5 C between 2.5 and 4.5 V. {yields} The discharge capacity of the material is strongly impacted by the reaction temperature. The powders sintered at 850 {sup o}C show the best electrochemical performance. -- Abstract: A low-temperature reaction route is introduced based on hydroxide precipitation method to synthesize the cathode material LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2}. The crystal structure and morphology of the prepared powder have been characterized by X-ray diffraction and Scan electron microscope, respectively. The charge-discharge tests were performed between 2.5 and 4.5 V. The discharge capacity of the material is strongly impacted by the reaction temperature. The powders sintered at 850 {sup o}C show the best electrochemical performance and the initial discharge capacity is about 160 mAh g{sup -1} at 5 C. Powder X-ray diffraction and Scan electron microscope results reveal that the excellent electrochemical performances should be ascribed to the lower precursor reaction temperature, the lower degree of cation mixing and analogous spherical small particles, which can improve the transfer of Li ions and electrons. All these results indicate that this material has potential application in lithium-ion batteries.« less
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