Mixed Ionic–Electronic Conductor of Perovskite LixLayMO3-δ toward Carbon-Free Cathode for Reversible Lithium–Air Batteries

Ma, Sang Bok; Kwon, Hyuk Jae; Kim, Mokwon; Bak, Seong‐Min; Lee, Hyunpyo; Ehrlich, Steven N.; Cho, Jeong‐Ju; Im, Dongmin; Seo, Dong‐Hwa

doi:10.1002/aenm.202001767

Title: Mixed Ionic–Electronic Conductor of Perovskite Li_xLa_yMO_3-δ toward Carbon-Free Cathode for Reversible Lithium–Air Batteries

Journal Article · Thu Aug 06 00:00:00 EDT 2020 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.202001767· OSTI ID:1647565

Ma, Sang Bok ^[1]; Kwon, Hyuk Jae ^[1]; Kim, Mokwon ^[1]; Bak, Seong‐Min ^[2]; Lee, Hyunpyo ^[1]; Ehrlich, Steven N. ^[3]; Cho, Jeong‐Ju ^[4]; Im, Dongmin ^[1];

^[5]

Samsung Electronics, Suwon (South Korea)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Samsung Research America, Burlington, MA (United States)
Samsung Research America, Burlington, MA (United States); Ulsan National Institute of Science and Technology (UNIST) (South Korea)

Mixed ionic–electronic conductors (MIECs) can play a pivotal role in achieving high energies and power densities in rechargeable batteries owing to their ability to simultaneously conduct ions and electrons. In our study, a new strategy is proposed wherein late 3d transition metals (TMs) are substituted into a perovskite Li-ion conductor to transform it into a Li-containing MIEC. First-principles calculations show that perovskite Li_xLa_yMO₃ with late 3d TMs have a low oxygen vacancy formation energy, implying high electron carrier concentrations corresponding to high electronic conductivity. The activation barriers for Li diffusion in Li_xLa_yMO₃ (M = Ti, Cr, Mn, Fe, and Co) are below 0.411 eV, resulting in high Li-ion conductivity. The designed perovskites of Li0.34La_0.55MnO_3-δ experimentally prove to have high electronic (2.04 × 10^-3 S cm^-1) and Li-ion (8.53 × 10^-5 S cm^-1) conductivities, and when applied in a carbon-free cathode of a Li–air cell, they deliver superior reversibility at 0.21 mAh cm^-2 over 100 charge/discharge cycles while avoiding the degradation associated with carbonaceous materials. Finally, this strategy enables the effective design of Li-conducting MIEC and reversible Li–air batteries.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; Korea Institute of Science and Technology Information

Grant/Contract Number:: SC0012704; KSC-2018-CRE-0006; 1.200092.01

OSTI ID:: 1647565

Alternate ID(s):: OSTI ID: 1646675

Report Number(s):: BNL-216257-2020-JAAM

Journal Information:: Advanced Energy Materials, Vol. 10, Issue 38; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 23 works

Citation information provided by
Web of Science

References (54)

Crystal Chemistry and Conductivity Studies in the System La0.5+x+yLi0.5−3xTi1−3yCr3yO3 Martínez-Sarrión, M. L.; Mestres, L.; Morales, M. Journal of Solid State Chemistry, Vol. 155, Issue 2 https://doi.org/10.1006/jssc.2000.8862	journal	December 2000
Electronic structure of CoO, Li-doped CoO, and ${LiCoO}_{2}$ van Elp, J.; Wieland, J. L.; Eskes, H. Physical Review B, Vol. 44, Issue 12 https://doi.org/10.1103/PhysRevB.44.6090	journal	September 1991
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution Grimaud, Alexis; May, Kevin J.; Carlton, Christopher E. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3439	journal	September 2013
Reactions in the Rechargeable Lithium–O ₂ Battery with Alkyl Carbonate Electrolytes Freunberger, Stefan A.; Chen, Yuhui; Peng, Zhangquan Journal of the American Chemical Society, Vol. 133, Issue 20 https://doi.org/10.1021/ja2021747	journal	May 2011
$K$ -edge absorption spectra of selected vanadium compounds Wong, J.; Lytle, F. W.; Messmer, R. P. Physical Review B, Vol. 30, Issue 10 https://doi.org/10.1103/PhysRevB.30.5596	journal	November 1984
Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials Ong, Shyue Ping; Chevrier, Vincent L.; Hautier, Geoffroy Energy & Environmental Science, Vol. 4, Issue 9 https://doi.org/10.1039/c1ee01782a	journal	January 2011
Algorithm for generating derivative structures Hart, Gus L. W.; Forcade, Rodney W. Physical Review B, Vol. 77, Issue 22 https://doi.org/10.1103/PhysRevB.77.224115	journal	June 2008
Low charge overpotentials in lithium–oxygen batteries based on tetraglyme electrolytes with a limited amount of water Wu, Shichao; Tang, Jing; Li, Fujun Chemical Communications, Vol. 51, Issue 94 https://doi.org/10.1039/C5CC06370A	journal	January 2015
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
High-throughput DFT calculations of formation energy, stability and oxygen vacancy formation energy of ABO3 perovskites Emery, Antoine A.; Wolverton, Chris Scientific Data, Vol. 4, Issue 1 https://doi.org/10.1038/sdata.2017.153	journal	October 2017
Computational understanding of Li-ion batteries Urban, Alexander; Seo, Dong-Hwa; Ceder, Gerbrand npj Computational Materials, Vol. 2, Issue 1 https://doi.org/10.1038/npjcompumats.2016.2	journal	March 2016
A novel solid-state Li–O ₂ battery with an integrated electrolyte and cathode structure Zhu, X. B.; Zhao, T. S.; Wei, Z. H. Energy & Environmental Science, Vol. 8, Issue 9 https://doi.org/10.1039/C5EE01604E	journal	January 2015
Genetics of superionic conductivity in lithium lanthanum titanates Jay, E. E.; Rushton, M. J. D.; Chroneos, A. Physical Chemistry Chemical Physics, Vol. 17, Issue 1 https://doi.org/10.1039/C4CP04834B	journal	January 2015
Synthesis, Phase Diagram, and Conductivity Study in a La0.5+x+yLi0.5−3xTi1−3yMn3yO3System Moreno, I.; Morales, M.; Marı́nez Sarrión, M. L. Journal of Solid State Chemistry, Vol. 140, Issue 2 https://doi.org/10.1006/jssc.1998.7904	journal	November 1998
Rechargeable lithium–air batteries: characteristics and prospects Imanishi, Nobuyuki; Yamamoto, Osamu Materials Today, Vol. 17, Issue 1 https://doi.org/10.1016/j.mattod.2013.12.004	journal	January 2014
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Highly efficient and stable solid-state Li–O 2 batteries using a perovskite solid electrolyte Le, Hang T. T.; Ngo, Duc Tung; Didwal, Pravin N. Journal of Materials Chemistry A, Vol. 7, Issue 7 https://doi.org/10.1039/C8TA10771H	journal	January 2019
Lithium Lanthanum Titanium Oxides: A Fast Ionic Conductive Coating for Lithium-Ion Battery Cathodes Qian, Danna; Xu, Bo; Cho, Hyung-Man Chemistry of Materials, Vol. 24, Issue 14 https://doi.org/10.1021/cm300929r	journal	July 2012
Improved initial guess for minimum energy path calculations Smidstrup, Søren; Pedersen, Andreas; Stokbro, Kurt The Journal of Chemical Physics, Vol. 140, Issue 21 https://doi.org/10.1063/1.4878664	journal	June 2014
Role of Defects in Low-Cost Perovskite Catalysts toward ORR and OER in Lithium–Oxygen Batteries Hegde, Guruprasad S.; Ghosh, Arpita; Badam, Rajashekar ACS Applied Energy Materials, Vol. 3, Issue 2 https://doi.org/10.1021/acsaem.9b01727	journal	January 2020
X-ray absorption and dichroism of transition metals and their compounds de Groot, F. M. F. Journal of Electron Spectroscopy and Related Phenomena, Vol. 67, Issue 4 https://doi.org/10.1016/0368-2048(93)02041-J	journal	August 1994
Predictive modeling and design rules for solid electrolytes Ceder, Gerbrand; Ong, Shyue Ping; Wang, Yan MRS Bulletin, Vol. 43, Issue 10 https://doi.org/10.1557/mrs.2018.210	journal	October 2018
The stability of organic solvents and carbon electrode in nonaqueous Li-O2 batteries Xu, Wu; Hu, Jianzhi; Engelhard, Mark H. Journal of Power Sources, Vol. 215 https://doi.org/10.1016/j.jpowsour.2012.05.021	journal	October 2012
On the Challenge of Electrolyte Solutions for Li–Air Batteries: Monitoring Oxygen Reduction and Related Reactions in Polyether Solutions by Spectroscopy and EQCM Sharon, Daniel; Etacheri, Vinodkumar; Garsuch, Arnd The Journal of Physical Chemistry Letters, Vol. 4, Issue 1 https://doi.org/10.1021/jz3017842	journal	December 2012
Characterization of Electronic and Ionic Transport in Li _1- _x Ni _0.33 Mn _0.33 Co _0.33 O ₂ (NMC ₃₃₃ ) and Li _1- _x Ni _0.50 Mn _0.20 Co _0.30 O ₂ (NMC ₅₂₃ ) as a Function of Li Content Amin, Ruhul; Chiang, Yet-Ming Journal of The Electrochemical Society, Vol. 163, Issue 8 https://doi.org/10.1149/2.0131608jes	journal	January 2016
Humidity effect on electrochemical performance of Li–O2 batteries Guo, Ziyang; Dong, Xiaoli; Yuan, Shouyi Journal of Power Sources, Vol. 264 https://doi.org/10.1016/j.jpowsour.2014.04.079	journal	October 2014
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries Kang, Kisuk; Shirley Meng, Ying; Breger, Julien Science, Vol. 311, Issue 5763, p. 977-980 https://doi.org/10.1126/science.1122152	journal	February 2006
Highly active Co-doped LaMnO 3 perovskite oxide and N-doped carbon nanotube hybrid bi-functional catalyst for rechargeable zinc–air batteries Lee, Dong Un; Park, Moon Gyu; Park, Hey Woong Electrochemistry Communications, Vol. 60 https://doi.org/10.1016/j.elecom.2015.08.001	journal	November 2015
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
New A-deficient perovskites in the series LixLa2/3Ti1-xFexO3 (0.12 ≤ x ≤ 0.33) and La(2+x)/3Ti1-xFexO3 (0.5 ≤ x ≤ 1.0) Crosnier-Lopez, M. P.; Duroy, H.; Calage, Y. Materials Research Bulletin, Vol. 36, Issue 3-4 https://doi.org/10.1016/S0025-5408(01)00518-9	journal	February 2001
Electronic Conductivity, Seebeck Coefficient, and Defect Structure of LaFeO3 Mizusaki, Junichiro; Sasamoto, Tadashi; Cannon, W. R. Journal of the American Ceramic Society, Vol. 65, Issue 8 https://doi.org/10.1111/j.1151-2916.1982.tb10485.x	journal	August 1982
Rechargeable Li ₂ O ₂ Electrode for Lithium Batteries Ogasawara, Takeshi; Débart, Aurélie; Holzapfel, Michael Journal of the American Chemical Society, Vol. 128, Issue 4 https://doi.org/10.1021/ja056811q	journal	February 2006
Rapid synthesis of room temperature ferromagnetic Ag-doped LaMnO3 perovskite phases by the solution combustion method Bellakki, Manjunath B.; Shivakumara, C.; Vasanthacharya, N. Y. Materials Research Bulletin, Vol. 45, Issue 11 https://doi.org/10.1016/j.materresbull.2010.06.063	journal	November 2010
Impact of air exposure and surface chemistry on Li–Li ₇ La ₃ Zr ₂ O ₁₂ interfacial resistance Sharafi, Asma; Yu, Seungho; Naguib, Michael Journal of Materials Chemistry A, Vol. 5, Issue 26 https://doi.org/10.1039/C7TA03162A	journal	January 2017
A Polymer Electrolyte-Based Rechargeable Lithium/Oxygen Battery Abraham, K. M.; Jiang, Z. Journal of The Electrochemical Society, Vol. 143, Issue 1, p. 1-5 https://doi.org/10.1149/1.1836378	journal	January 1996
Conduction in LaCo $O_{3}$ by small-polaron hopping below room temperature Iguchi, E.; Ueda, K.; Jung, W. H. Physical Review B, Vol. 54, Issue 24 https://doi.org/10.1103/PhysRevB.54.17431	journal	December 1996
Factors that affect Li mobility in layered lithium transition metal oxides Kang, Kisuk; Ceder, Gerbrand Physical Review B, Vol. 74, Issue 9 https://doi.org/10.1103/PhysRevB.74.094105	journal	September 2006
Formation enthalpies by mixing GGA and GGA $+$ $U$ calculations Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping Physical Review B, Vol. 84, Issue 4 https://doi.org/10.1103/PhysRevB.84.045115	journal	July 2011
Magnetic properties and colossal magnetoresistance of La(Ca)Mn $O_{3}$ materials doped with Fe Ahn, K. H.; Wu, X. W.; Liu, K. Physical Review B, Vol. 54, Issue 21 https://doi.org/10.1103/PhysRevB.54.15299	journal	December 1996
Crystal structure of the mixed conductors phases, Li0.5-3xLa0.5+x+yTi1-3yM3yO3 (M=Mn, Cr) with x=0.133 and y=0.20 Morales, Manuel; Mestres, Lourdes; Dlouhá, Maja Journal of Materials Chemistry, Vol. 8, Issue 12 https://doi.org/10.1039/a804764b	journal	January 1998
Effect of average and local structures on lithium ion conductivity in La2/3−xLi3xTiO3 Okumura, Toyoki; Ina, Toshiaki; Orikasa, Yuki Journal of Materials Chemistry, Vol. 21, Issue 27 https://doi.org/10.1039/c0jm04372a	journal	January 2011
Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors Deng, Zhi; Zhu, Zhuoying; Chu, Iek-Heng Chemistry of Materials, Vol. 29, Issue 1 https://doi.org/10.1021/acs.chemmater.6b02648	journal	September 2016
Electrochemical performance of an all-solid-state lithium–oxygen battery under humidified oxygen Suzuki, Y.; Watanabe, K.; Sakuma, S. Solid State Ionics, Vol. 289 https://doi.org/10.1016/j.ssi.2016.03.003	journal	June 2016
The water catalysis at oxygen cathodes of lithium–oxygen cells Li, Fujun; Wu, Shichao; Li, De Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8843	journal	July 2015
Porous perovskite CaMnO ₃ as an electrocatalyst for rechargeable Li–O ₂ batteries Han, Xiaopeng; Hu, Yuxiang; Yang, Jingang Chem. Commun., Vol. 50, Issue 12 https://doi.org/10.1039/C3CC48207C	journal	January 2014
High ionic conductivity in lithium lanthanum titanate Inaguma, Yoshiyuki; Liquan, Chen; Itoh, Mitsuru Solid State Communications, Vol. 86, Issue 10, p. 689-693 https://doi.org/10.1016/0038-1098(93)90841-A	journal	June 1993
The exploration of Lanthanum based perovskites and their complementary electrolytes for the supercapacitor applications Arjun, Nadarajan; Pan, Guan-Tin; Yang, Thomas C. K. Results in Physics, Vol. 7 https://doi.org/10.1016/j.rinp.2017.02.013	journal	January 2017
Electrocatalytic performances of LaNi1−xMgxO3 perovskite oxides as bi-functional catalysts for lithium air batteries Du, Zhenzhen; Yang, Peng; Wang, Long Journal of Power Sources, Vol. 265 https://doi.org/10.1016/j.jpowsour.2014.04.096	journal	November 2014
Oxidation energies of transition metal oxides within the $GGA + U$ framework Wang, Lei; Maxisch, Thomas; Ceder, Gerbrand Physical Review B, Vol. 73, Issue 19 https://doi.org/10.1103/PhysRevB.73.195107	journal	May 2006
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
Influences of carrier concentration and site percolation on lithium ion conductivity in perovskite-type oxides Inaguma, Yoshiyuki; Itoh, Mitsuru Solid State Ionics, Vol. 86-88 https://doi.org/10.1016/0167-2738(96)00100-2	journal	July 1996
Structural phenomena associated with the spin-state transition in ${LaCoO}_{3}$ Radaelli, P. G.; Cheong, S. -W. Physical Review B, Vol. 66, Issue 9 https://doi.org/10.1103/PhysRevB.66.094408	journal	September 2002
Solvents’ Critical Role in Nonaqueous Lithium–Oxygen Battery Electrochemistry McCloskey, B. D.; Bethune, D. S.; Shelby, R. M. The Journal of Physical Chemistry Letters, Vol. 2, Issue 10, p. 1161-1166 https://doi.org/10.1021/jz200352v	journal	May 2011

Similar Records

Enhanced Mixed Electronic-Ionic Conductors through Cation Ordering

Technical Report · Sun Aug 31 00:00:00 EDT 2014 · OSTI ID:1647565

Jacobson, Allan J.; Morgan, Dane; Grey, Clare

Freestanding 1T MoS₂/graphene heterostructures as a highly efficient electrocatalyst for lithium polysulfides in Li–S batteries

Journal Article · Tue Nov 27 00:00:00 EST 2018 · Energy & Environmental Science · OSTI ID:1647565

He, Jiarui; Hartmann, Gregory; Lee, Myungsuk; +3 more

LiSr{sub 1.65}{open_square}{sub 0.35}B{sub 1.3}B{prime}{sub 1.7}O{sub 9} (B = Ti, Zr; B{prime} = Nb, Ta): New lithium ion conductors based on the perovskite structure

Journal Article · Mon Mar 01 00:00:00 EST 1999 · Chemistry of Materials · OSTI ID:1647565

Thangadurai, V; Shukla, A K; Gopalakrishnan, J

Related Subjects

36 MATERIALS SCIENCE
lithium diffusion barriers
lithium-air batteries
mixed ionic-electronic conductors
perovskites

Title: Mixed Ionic–Electronic Conductor of Perovskite LixLayMO3-δ toward Carbon-Free Cathode for Reversible Lithium–Air Batteries

Citation Formats

References (54)

Similar Records

Related Subjects

Title: Mixed Ionic–Electronic Conductor of Perovskite Li_xLa_yMO_3-δ toward Carbon-Free Cathode for Reversible Lithium–Air Batteries