Direct Observation of Reversible Magnesium Ion Intercalation into a Spinel Oxide Host

Kim, Chunjoong; Phillips, Patrick J.; Key, Baris; Yi, Tanghong; Nordlund, Dennis; Yu, Young-Sang; Bayliss, Ryan D.; Han, Sang-Don; He, Meinan; Zhang, Zhengcheng; Burrell, Anthony K.; Klie, Robert F.; Cabana, Jordi

doi:10.1002/adma.201500083

Title: Direct Observation of Reversible Magnesium Ion Intercalation into a Spinel Oxide Host

Journal Article · Fri Apr 17 00:00:00 EDT 2015 · Advanced Materials

DOI:https://doi.org/10.1002/adma.201500083· OSTI ID:1248946

Kim, Chunjoong ^[1]; Phillips, Patrick J. ^[1]; Key, Baris ^[2]; Yi, Tanghong ^[1]; Nordlund, Dennis ^[3]; Yu, Young-Sang ^[4]; Bayliss, Ryan D. ^[1]; Han, Sang-Don ^[2]; He, Meinan ^[5]; Zhang, Zhengcheng ^[2]; Burrell, Anthony K. ^[2]; Klie, Robert F. ^[1]; Cabana, Jordi ^[1]

Univ. of Illinois at Chicago, Chicago IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Univ. of Illinois at Chicago, Chicago IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Mechanical Engineering, Worcester Polytechnic Institute, Worcester MA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Direct evidence of Mg2+ intercalation into a spinel-type Mn2O4 is provided. By combining tools with different sensitivities, from atomic-resolution X-ray spectroscopy to bulk X-ray diffraction, it is demonstrated that Mg2+ reversibly occupies the tetrahedral sites of the spinel structure through the reduction of Mn when the electrochemical reaction is performed.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: AC02-06CH11357; SC0001294

OSTI ID:: 1248946

Journal Information:: Advanced Materials, Vol. 27, Issue 22; ISSN 0935-9648

Publisher:: Wiley

Country of Publication:: United States

Language:: English

References (43)

Lithium Batteries and Cathode Materials Whittingham, M. Stanley Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302 https://doi.org/10.1021/cr020731c	journal	October 2004
Evolution of Strategies for Modern Rechargeable Batteries Goodenough, John B. Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar2002705	journal	June 2012
Electric Vehicle Battery Technologies Young, Kwo; Wang, Caisheng; Wang, Le Yi Electric Vehicle Integration into Modern Power Networks https://doi.org/10.1007/978-1-4614-0134-6_2	book	October 2012
Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries Thackeray, Michael M.; Wolverton, Christopher; Isaacs, Eric D. Energy & Environmental Science, Vol. 5, Issue 7 https://doi.org/10.1039/c2ee21892e	journal	January 2012
Ultimate Limits to Intercalation Reactions for Lithium Batteries Whittingham, M. Stanley Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr5003003	journal	October 2014
Li–O₂ and Li–S batteries with high energy storage Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J. Nature Materials, Vol. 11, Issue 1, p. 19-29 https://doi.org/10.1038/nmat3191	journal	January 2012
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
The rechargeable revolution: A better battery Van Noorden, Richard Nature, Vol. 507, Issue 7490 https://doi.org/10.1038/507026a	journal	March 2014
Mg rechargeable batteries: an on-going challenge Yoo, Hyun Deog; Shterenberg, Ivgeni; Gofer, Yosef Energy & Environmental Science, Vol. 6, Issue 8, p. 2265-2279 https://doi.org/10.1039/c3ee40871j	journal	January 2013
Potential positive electrodes for high-voltage magnesium-ion batteries Ichitsubo, Tetsu; Adachi, Takero; Yagi, Shunsuke Journal of Materials Chemistry, Vol. 21, Issue 32 https://doi.org/10.1039/c1jm11793a	journal	January 2011
High capacity positive electrodes for secondary Mg-ion batteries Rasul, Shahid; Suzuki, Shinya; Yamaguchi, Shu Electrochimica Acta, Vol. 82 https://doi.org/10.1016/j.electacta.2012.03.095	journal	November 2012
Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond Muldoon, John; Bucur, Claudiu B.; Gregory, Thomas Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500049y	journal	October 2014
Investigation of Yttrium and Polyvalent Ion Intercalation into Nanocrystalline Vanadium Oxide Amatucci, G. G.; Badway, F.; Singhal, A. Journal of The Electrochemical Society, Vol. 148, Issue 8 https://doi.org/10.1149/1.1383777	journal	January 2001
Chemical intercalation of magnesium into solid hosts Bruce, Peter G.; Krok, Franciszek; Nowinski, Jan Journal of Materials Chemistry, Vol. 1, Issue 4 https://doi.org/10.1039/jm9910100705	journal	January 1991
On the Way to Rechargeable Mg Batteries: The Challenge of New Cathode Materials ^† Levi, E.; Gofer, Y.; Aurbach, D. Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm9016497	journal	February 2010
Progress in nonaqueous magnesium electrochemistry Amir, N.; Vestfrid, Y.; Chusid, O. Journal of Power Sources, Vol. 174, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.06.206	journal	December 2007
Prototype systems for rechargeable magnesium batteries Aurbach, D.; Lu, Z.; Schechter, A. Nature, Vol. 407, Issue 6805, p. 724-727 https://doi.org/10.1038/35037553	journal	October 2000
Lithium insertion into manganese spinels Thackeray, M. M.; David, W. I. F.; Bruce, P. G. Materials Research Bulletin, Vol. 18, Issue 4, p. 461-472 https://doi.org/10.1016/0025-5408(83)90138-1	journal	April 1983
Investigation of the intercalation of polyvalent cations (Mg2+, Zn2+) into λ-MnO2 for rechargeable aqueous battery Yuan, Congli; Zhang, Ying; Pan, Yue Electrochimica Acta, Vol. 116 https://doi.org/10.1016/j.electacta.2013.11.090	journal	January 2014
Electrochemical Conversion of LiMn[sub 2]O[sub 4] to MgMn[sub 2]O[sub 4] in Aqueous Electrolytes Sinha, Nupur Nikkan; Munichandraiah, N. Electrochemical and Solid-State Letters, Vol. 11, Issue 11 https://doi.org/10.1149/1.2972990	journal	January 2008
Structural Evolution of Li[sub x]Mn[sub 2]O[sub 4] in Lithium-Ion Battery Cells Measured In Situ Using Synchrotron X-Ray Diffraction Techniques Mukerjee, S. Journal of The Electrochemical Society, Vol. 145, Issue 2 https://doi.org/10.1149/1.1838286	journal	January 1998
Structural change of the LiMn2O4 spinel structure induced by extraction of lithium Kanamura, Kiyoshi; Naito, Hidetoshi; Yao, Takeshi Journal of Materials Chemistry, Vol. 6, Issue 1 https://doi.org/10.1039/jm9960600033	journal	January 1996
Proton insertion and lithium-proton exchange in spinel lithium manganates Ammundsen, Brett; Aitchison, Phillip B.; Burns, Gary R. Solid State Ionics, Vol. 97, Issue 1-4 https://doi.org/10.1016/S0167-2738(97)00065-9	journal	May 1997
Mechanism of Proton Insertion and Characterization of the Proton Sites in Lithium Manganate Spinels Ammundsen, Brett; Jones, Deborah J.; Roziere, Jacques Chemistry of Materials, Vol. 7, Issue 11 https://doi.org/10.1021/cm00059a024	journal	November 1995
Synthesis of MnO[sub 2] Phases from LiMn[sub 2]O[sub 4] in Aqueous Acidic Media Larcher, D. Journal of The Electrochemical Society, Vol. 145, Issue 10 https://doi.org/10.1149/1.1838818	journal	January 1998
Water Oxidation by λ-MnO ₂ : Catalysis by the Cubical Mn ₄ O ₄ Subcluster Obtained by Delithiation of Spinel LiMn ₂ O ₄ Robinson, David M.; Go, Yong Bok; Greenblatt, Martha Journal of the American Chemical Society, Vol. 132, Issue 33 https://doi.org/10.1021/ja1055615	journal	August 2010
Spinel compounds as multivalent battery cathodes: a systematic evaluation based on ab initio calculations Liu, Miao; Rong, Ziqin; Malik, Rahul Energy & Environmental Science, Vol. 8, Issue 3 https://doi.org/10.1039/C4EE03389B	journal	January 2015
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav Computational Materials Science, Vol. 68 https://doi.org/10.1016/j.commatsci.2012.10.028	journal	February 2013
In Situ Mn K-edge X-ray Absorption Spectroscopy Studies of Electrodeposited Manganese Oxide Films for Electrochemical Capacitors Nam, Kyung-Wan; Kim, Min Gyu; Kim, Kwang-Bum The Journal of Physical Chemistry C, Vol. 111, Issue 2 https://doi.org/10.1021/jp063130o	journal	January 2007
Nanostructured manganese oxide clusters supported on mesoporous silica as efficient oxygen-evolving catalysts Jiao, Feng; Frei, Heinz Chemical Communications, Vol. 46, Issue 17 https://doi.org/10.1039/b921820c	journal	January 2010
High resolution electron energy loss spectroscopy of manganese oxides: Application to Mn3O4 nanoparticles Laffont, L.; Gibot, P. Materials Characterization, Vol. 61, Issue 11 https://doi.org/10.1016/j.matchar.2010.09.001	journal	November 2010
Key electronic states in lithium battery materials probed by soft X-ray spectroscopy Yang, Wanli; Liu, Xiaosong; Qiao, Ruimin Journal of Electron Spectroscopy and Related Phenomena, Vol. 190 https://doi.org/10.1016/j.elspec.2013.03.008	journal	October 2013
Oxygen 1 s x-ray-absorption edges of transition-metal oxides de Groot, F. M. F.; Grioni, M.; Fuggle, J. C. Physical Review B, Vol. 40, Issue 8 https://doi.org/10.1103/PhysRevB.40.5715	journal	September 1989
Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides Qiao, Ruimin; Chin, Timothy; Harris, Stephen J. Current Applied Physics, Vol. 13, Issue 3 https://doi.org/10.1016/j.cap.2012.09.017	journal	May 2013
NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries Grey, Clare P.; Dupré, Nicolas Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020734p	journal	October 2004
Understanding the NMR shifts in paramagnetic transition metal oxides using density functional theory calculations Carlier, D.; Ménétrier, M.; Grey, C. P. Physical Review B, Vol. 67, Issue 17 https://doi.org/10.1103/PhysRevB.67.174103	journal	May 2003
Solid-state magnesium-25 n.m.r. spectroscopy Dupree, R.; Smith, M. E. Journal of the Chemical Society, Chemical Communications, Issue 22 https://doi.org/10.1039/c39880001483	journal	January 1988
Solid-state 25Mg QCPMG NMR of bis(cyclopentadienyl)magnesium Hung, Ivan; Schurko, Robert W. Solid State Nuclear Magnetic Resonance, Vol. 24, Issue 2-3 https://doi.org/10.1016/S0926-2040(03)00050-X	journal	September 2003
Structural and Transport Properties of Mg1−xMnxMn2O4±δ Spinels Malavasi, Lorenzo; Ghigna, Paolo; Chiodelli, Gaetano Journal of Solid State Chemistry, Vol. 166, Issue 1 https://doi.org/10.1006/jssc.2002.9577	journal	June 2002
Lithium MAS NMR studies of cathode materials for lithium-ion batteries Grey, Clare P.; Lee, Young Joo Solid State Sciences, Vol. 5, Issue 6 https://doi.org/10.1016/S1293-2558(03)00113-4	journal	June 2003
Understanding the Electrochemical Mechanism of K-αMnO ₂ for Magnesium Battery Cathodes Arthur, Timothy S.; Zhang, Ruigang; Ling, Chen ACS Applied Materials & Interfaces, Vol. 6, Issue 10 https://doi.org/10.1021/am5015327	journal	May 2014
A New Silicon Drift Detector for High Spatial Resolution STEM-XEDS: Performance and Applications Phillips, Patrick J.; Paulauskas, Tadas; Rowlands, Neil Microscopy and Microanalysis, Vol. 20, Issue 4 https://doi.org/10.1017/S1431927614001639	journal	July 2014

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Title: Direct Observation of Reversible Magnesium Ion Intercalation into a Spinel Oxide Host

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