Multivalent Electrochemistry of Spinel MgxMn3–xO4 Nanocrystals

Kim, Chunjoong; Adil, Abdullah A.; Bayliss, Ryan D.; Kinnibrugh, Tiffany L.; Lapidus, Saul H.; Nolis, Gene M.; Freeland, John W.; Phillips, Patrick J.; Yi, Tanghong; Yoo, Hyun Deog; Kwon, Bob Jin; Yu, Young -Sang; Klie, Robert; Chupas, Peter J.; Chapman, Karena W.; Cabana, Jordi

doi:10.1021/acs.chemmater.7b03640

Title: Multivalent Electrochemistry of Spinel Mg_xMn_3–xO₄ Nanocrystals

Journal Article · Tue Feb 20 00:00:00 EST 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.7b03640· OSTI ID:1461417

Kim, Chunjoong ^[1]; Adil, Abdullah A. ^[2]; Bayliss, Ryan D. ^[2]; Kinnibrugh, Tiffany L. ^[3]; Lapidus, Saul H. ^[3]; Nolis, Gene M. ^[2]; Freeland, John W. ^[3]; Phillips, Patrick J. ^[4]; Yi, Tanghong ^[2];

^[2]; Kwon, Bob Jin ^[2]; Yu, Young -Sang ^[5]; Klie, Robert ^[4]; Chupas, Peter J. ^[3];

^[3];

^[2]

Univ. of Illinois at Chicago, Chicago, IL (United States); Chungnam National Univ., Daejeon (South Korea); Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Illinois at Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Illinois at Chicago, Chicago, IL (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Oxides undergoing reversible electrochemical cycling of Mg²⁺ ions would enable novel battery concepts beyond Li⁺, capable of storing large amounts of energy. However, materials showing this chemical reactivity are scarce. Suitable candidates require small particles to shorten transport lengths, together with chemically complex structures that promote cation mobility, such as spinel. These goals pose a challenge for materials chemists. Here, nanocrystals of spinel-type Mg_0.5Mn_2.5O₄ were prepared using colloidal synthesis, and their electrochemical activity is presented. Cycling in an aqueous Mg²⁺ electrolyte led to a reversible transformation between a reduced spinel and an oxidized layered framework. This reaction involves large amounts of capacity because of the full oxidation to Mn⁴⁺, through the extraction of both Mg²⁺ and, in the first cycle, Mn²⁺ ions. Re-formation of the spinel upon reduction resulted in enrichment with Mg²⁺, indicating that its insertion is more favorable than that of Mn²⁺. Incorporation of water into the structure was not indispensable for the transformation, as revealed by experiments in non-aqueous electrolytes and infrared spectroscopy. Lastly, the findings open the door for the use of similar nanocrystals in Mg batteries provided that electrolytes with suitable anodic stability are discovered, thereby identifying novel routes toward electrode materials for batteries with high energy.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1461417

Journal Information:: Chemistry of Materials, Vol. 30, Issue 5; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 20 works

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References (32)

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
Materials Design Rules for Multivalent Ion Mobility in Intercalation Structures Rong, Ziqin; Malik, Rahul; Canepa, Pieremanuele Chemistry of Materials, Vol. 27, Issue 17 https://doi.org/10.1021/acs.chemmater.5b02342	journal	August 2015
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
Direct Observation of Reversible Magnesium Ion Intercalation into a Spinel Oxide Host Kim, Chunjoong; Phillips, Patrick J.; Key, Baris Advanced Materials, Vol. 27, Issue 22 https://doi.org/10.1002/adma.201500083	journal	April 2015
A neutron diffraction study of the cation migration in MgMn2O4 Radhakrishnan, N. K.; Biswas, A. B. Physica Status Solidi (a), Vol. 37, Issue 2 https://doi.org/10.1002/pssa.2210370245	journal	October 1976
Atomic and molecular clusters in membrane mimetic chemistry Fendler, Janos H. Chemical Reviews, Vol. 87, Issue 5 https://doi.org/10.1021/cr00081a002	journal	October 1987
The preparation of monodisperse colloidal metal particles from microemulsions Boutonnet, Magali; Kizling, Jerzy; Stenius, Per Colloids and Surfaces, Vol. 5, Issue 3 https://doi.org/10.1016/0166-6622(82)80079-6	journal	November 1982
Synthesis of Highly Crystalline and Monodisperse Maghemite Nanocrystallites without a Size-Selection Process Hyeon, Taeghwan; Lee, Su Seong; Park, Jongnam Journal of the American Chemical Society, Vol. 123, Issue 51, p. 12798-12801 https://doi.org/10.1021/ja016812s	journal	December 2001
Ultra-large-scale syntheses of monodisperse nanocrystals Park, Jongnam; An, Kwangjin; Hwang, Yosun Nature Materials, Vol. 3, Issue 12 https://doi.org/10.1038/nmat1251	journal	November 2004
Stabilization of Battery Electrode/Electrolyte Interfaces Employing Nanocrystals with Passivating Epitaxial Shells Kim, Chunjoong; Phillips, Patrick J.; Xu, Linping Chemistry of Materials, Vol. 27, Issue 1 https://doi.org/10.1021/cm503615w	journal	December 2014
On the Utility of Spinel Oxide Hosts for Magnesium-Ion Batteries Knight, James C.; Therese, Soosairaj; Manthiram, Arumugam ACS Applied Materials & Interfaces, Vol. 7, Issue 41 https://doi.org/10.1021/acsami.5b06179	journal	October 2015
Atomic defects during ordering transitions in LiNi _0.5 Mn _1.5 O ₄ and their relationship with electrochemical properties Casas-Cabanas, Montse; Kim, Chunjoong; Rodríguez-Carvajal, Juan Journal of Materials Chemistry A, Vol. 4, Issue 21 https://doi.org/10.1039/C6TA00424E	journal	January 2016
A dedicated powder diffraction beamline at the Advanced Photon Source: Commissioning and early operational results Wang, Jun; Toby, Brian H.; Lee, Peter L. Review of Scientific Instruments, Vol. 79, Issue 8 https://doi.org/10.1063/1.2969260	journal	August 2008
A twelve-analyzer detector system for high-resolution powder diffraction Lee, Peter L.; Shu, Deming; Ramanathan, Mohan Journal of Synchrotron Radiation, Vol. 15, Issue 5 https://doi.org/10.1107/S0909049508018438	journal	July 2008
Applications of an amorphous silicon-based area detector for high-resolution, high-sensitivity and fast time-resolved pair distribution function measurements Chupas, Peter J.; Chapman, Karena W.; Lee, Peter L. Journal of Applied Crystallography, Vol. 40, Issue 3 https://doi.org/10.1107/S0021889807007856	journal	May 2007
Rapid-acquisition pair distribution function (RA-PDF) analysis Chupas, Peter J.; Qiu, Xiangyun; Hanson, Jonathan C. Journal of Applied Crystallography, Vol. 36, Issue 6, p. 1342-1347 https://doi.org/10.1107/S0021889803017564	journal	November 2003
Two-dimensional detector software: From real detector to idealised image or two-theta scan Hammersley, A. P.; Svensson, S. O.; Hanfland, M. High Pressure Research, Vol. 14, Issue 4-6, p. 235-248 https://doi.org/10.1080/08957959608201408	journal	January 1996
PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L. Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678 https://doi.org/10.1107/S0021889804011744	journal	July 2004
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals Farrow, C. L.; Juhas, P.; Liu, J. W. Journal of Physics: Condensed Matter, Vol. 19, Issue 33 https://doi.org/10.1088/0953-8984/19/33/335219	journal	July 2007
A profile refinement method for nuclear and magnetic structures Rietveld, H. M. Journal of Applied Crystallography, Vol. 2, Issue 2, p. 65-71 https://doi.org/10.1107/S0021889869006558	journal	June 1969
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Manganese oxides for lithium batteries Thackeray, Michael M. Progress in Solid State Chemistry, Vol. 25, Issue 1-2 https://doi.org/10.1016/S0079-6786(97)81003-5	journal	January 1997
Phase Diagram of Li−Mn−O Spinel in Air Paulsen, J. M.; Dahn, J. R. Chemistry of Materials, Vol. 11, Issue 11 https://doi.org/10.1021/cm9900960	journal	November 1999
Tuning the Electrocatalytic Water Oxidation Properties of AB ₂ O ₄ Spinel Nanocrystals: A (Li, Mg, Zn) and B (Mn, Co) Site Variants of LiMn ₂ O ₄ Cady, Clyde W.; Gardner, Graeme; Maron, Zachary O. ACS Catalysis, Vol. 5, Issue 6 https://doi.org/10.1021/acscatal.5b00265	journal	May 2015
Layered-to-Spinel Phase Transition in Li[sub x]MnO[sub 2] Reed, J.; Ceder, G.; Van Der Ven, A. Electrochemical and Solid-State Letters, Vol. 4, Issue 6 https://doi.org/10.1149/1.1368896	journal	January 2001
The High Performance of Crystal Water Containing Manganese Birnessite Cathodes for Magnesium Batteries Nam, Kwan Woo; Kim, Sangryun; Lee, Soyeon Nano Letters, Vol. 15, Issue 6 https://doi.org/10.1021/acs.nanolett.5b01109	journal	May 2015
Birnessite manganese dioxide synthesized via a sol—gel process: a new rechargeable cathodic material for lithium batteries Bach, S.; Pereira-Ramos, J. P.; Baffier, N. Electrochimica Acta, Vol. 36, Issue 10 https://doi.org/10.1016/0013-4686(91)85012-V	journal	January 1991
Synthesis, Characterization, and Electrochemical Properties of Magnesium Birnessite and Zinc Chalcophanite Prepared by a Low-Temperature Route Aronson, Blake J.; Kinser, Andrew K.; Passerini, Stefano Chemistry of Materials, Vol. 11, Issue 4 https://doi.org/10.1021/cm9805828	journal	April 1999
Practical Stability Limits of Magnesium Electrolytes Lipson, Albert L.; Han, Sang-Don; Pan, Baofei Journal of The Electrochemical Society, Vol. 163, Issue 10 https://doi.org/10.1149/2.0451610jes	journal	January 2016
Mn and Co Charge and Spin Evolutions in LaMn _{1– x} Co _x O ₃ Nanoparticles Ghiasi, Mahnaz; Delgado-Jaime, Mario Ulises; Malekzadeh, Azim The Journal of Physical Chemistry C, Vol. 120, Issue 15 https://doi.org/10.1021/acs.jpcc.6b00949	journal	April 2016
Sol−Gel Synthesis of Layered Birnessite-Type Manganese Oxides Ching, Stanton; Petrovay, Diana J.; Jorgensen, Matthew L. Inorganic Chemistry, Vol. 36, Issue 5 https://doi.org/10.1021/ic961088d	journal	February 1997
Intercalation of Water in P2, T2 and O2 Structure A _z [Co _x Ni _1/3- _x Mn _2/3 ]O ₂ Lu, Zhonghua; Dahn, J. R. Chemistry of Materials, Vol. 13, Issue 4 https://doi.org/10.1021/cm000721x	journal	April 2001

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