Intercalation of Ca into a Highly Defective Manganese Oxide at Room Temperature

Kwon, Bob Jin; Yin, Liang; Bartel, Christopher J.; Kumar, Khagesh; Parajuli, Prakash; Gim, Jihyeon; Kim, Sanghyeon; Wu, Yimin A.; Klie, Robert F.; Lapidus, Saul H.; Key, Baris; Ceder, Gerbrand; Cabana, Jordi

doi:10.1021/acs.chemmater.1c03803

Title: Intercalation of Ca into a Highly Defective Manganese Oxide at Room Temperature

Journal Article · 10 January 2022 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.1c03803 · OSTI ID:1879873

^[1]; Yin, Liang ^[1];

^[2]; Kumar, Khagesh ^[3];

^[4]; Gim, Jihyeon ^[1];

^[1];

^[4];

^[1];

^[2];

^[4]

Argonne National Lab. (ANL), Lemont, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of Illinois, Chicago, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Illinois, Chicago, IL (United States)

The utilization of oxide frameworks as intercalation cathodes for non-aqueous Ca-ion batteries potentially unlocks a new energy storage system that delivers high energy density. However, the slow kinetics of Ca²⁺ in oxide electrodes strongly handicaps their activity and reversibility at room temperature. Here, nanocrystals of layered MnO_x containing a high concentration of atomic defects and lattice water are shown to have remarkable electrochemical activity towards Ca²⁺, amounting to a capacity of ~130 mAh/g at room temperature. Multimodal characterization revealed the notable degree of intercalation by probing the structural, compositional and redox changes undertaken by the defective MnO_x nanocrystals. The results suggest that the existence of atomic defects and lattice water played a role in improving Ca²⁺ diffusivity in the oxide. These outcomes reaffirm the prospects for functional Ca-ion batteries using oxide cathodes under moderate conditions.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Joint Center for Energy Storage Research (JCESR); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357; AC02-05CH11231

OSTI ID:: 1879873

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 2 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (53)

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
Calcium-Ion Batteries: Current State-of-the-Art and Future Perspectives Gummow, Rosalind J.; Vamvounis, George; Kannan, M. Bobby Advanced Materials, Vol. 30, Issue 39 https://doi.org/10.1002/adma.201801702	journal	July 2018
Stable and High‐Power Calcium‐Ion Batteries Enabled by Calcium Intercalation into Graphite Park, Jooha; Xu, Zheng‐Long; Yoon, Gabin Advanced Materials, Vol. 32, Issue 4 https://doi.org/10.1002/adma.201904411	journal	November 2019
X-ray Absorption Studies in Spinel-Type LiMn2O4 Liu, R. S.; Jang, L. Y.; Chen, J. M. Journal of Solid State Chemistry, Vol. 128, Issue 2 https://doi.org/10.1006/jssc.1997.7291	journal	February 1997
X-ray absorption spectroscopy to analyze nuclear geometry and electronic structure of biological metal centers?potential and questions examined with special focus on the tetra-nuclear manganese complex of oxygenic photosynthesis Dau, Holger; Liebisch, Peter; Haumann, Michael Analytical and Bioanalytical Chemistry, Vol. 376, Issue 5 https://doi.org/10.1007/s00216-003-1982-2	journal	July 2003
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Nucleation and growth of todorokite from birnessite: Implications for trace-metal cycling in marine sediments Atkins, Amy L.; Shaw, Samuel; Peacock, Caroline L. Geochimica et Cosmochimica Acta, Vol. 144 https://doi.org/10.1016/j.gca.2014.08.014	journal	November 2014
On the use of activated carbon as a quasi-reference electrode in non-aqueous electrolyte solutions Ruch, P. W.; Cericola, D.; Hahn, M. Journal of Electroanalytical Chemistry, Vol. 636, Issue 1-2 https://doi.org/10.1016/j.jelechem.2009.09.007	journal	November 2009
Investigation of electrochemical calcium-ion energy storage mechanism in potassium birnessite Hyoung, Jooeun; Heo, Jongwook W.; Hong, Seung-Tae Journal of Power Sources, Vol. 390 https://doi.org/10.1016/j.jpowsour.2018.04.050	journal	June 2018
Zn ion diffusion in spinel-type cathode materials for rechargeable batteries: the role of point defects Morando, Carolina; Cofrancesco, Pacifico; Tealdi, Cristina Materials Today Communications, Vol. 25 https://doi.org/10.1016/j.mtcomm.2020.101478	journal	December 2020
Evaluation of counter and reference electrodes for the investigation of Ca battery materials Liu, Xu; Elia, Giuseppe Antonio; Passerini, Stefano Journal of Power Sources Advances, Vol. 2 https://doi.org/10.1016/j.powera.2020.100008	journal	April 2020
Intercalation of Mg into a Few-Layer Phyllomanganate in Nonaqueous Electrolytes at Room Temperature Kwon, Bob Jin; Kim, Chunjoong; Jokisaari, Jacob R. Chemistry of Materials, Vol. 32, Issue 14 https://doi.org/10.1021/acs.chemmater.0c01305	journal	June 2020
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
Rechargeable Ca-Ion Batteries: A New Energy Storage System Lipson, Albert L.; Pan, Baofei; Lapidus, Saul H. Chemistry of Materials, Vol. 27, Issue 24 https://doi.org/10.1021/acs.chemmater.5b04027	journal	December 2015
A Joint Computational and Experimental Evaluation of CaMn ₂ O ₄ Polymorphs as Cathode Materials for Ca Ion Batteries Dompablo, M. Elena Arroyo-de; Krich, Christopher; Nava-Avendaño, Jessica Chemistry of Materials, Vol. 28, Issue 19 https://doi.org/10.1021/acs.chemmater.6b02146	journal	September 2016
Mechanism of Zn Insertion into Nanostructured δ-MnO ₂ : A Nonaqueous Rechargeable Zn Metal Battery Han, Sang-Don; Kim, Soojeong; Li, Dongguo Chemistry of Materials, Vol. 29, Issue 11 https://doi.org/10.1021/acs.chemmater.7b00852	journal	May 2017
Influence of Inversion on Mg Mobility and Electrochemistry in Spinels Sai Gautam, Gopalakrishnan; Canepa, Pieremanuele; Urban, Alexander Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b02820	journal	September 2017
Electrochemical Intercalation of Calcium and Magnesium in TiS ₂ : Fundamental Studies Related to Multivalent Battery Applications Tchitchekova, Deyana S.; Ponrouch, Alexandre; Verrelli, Roberta Chemistry of Materials, Vol. 30, Issue 3 https://doi.org/10.1021/acs.chemmater.7b04406	journal	January 2018
Methods and Protocols for Reliable Electrochemical Testing in Post-Li Batteries (Na, K, Mg, and Ca) Dugas, Romain; Forero-Saboya, Juan D.; Ponrouch, Alexandre Chemistry of Materials, Vol. 31, Issue 21 https://doi.org/10.1021/acs.chemmater.9b02776	journal	October 2019
Noncrystalline Nanocomposites as a Remedy for the Low Diffusivity of Multivalent Ions in Battery Cathodes Orikasa, Yuki; Kisu, Kazuaki; Iwama, Etsuro Chemistry of Materials, Vol. 32, Issue 3 https://doi.org/10.1021/acs.chemmater.9b03665	journal	January 2020
Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges Canepa, Pieremanuele; Sai Gautam, Gopalakrishnan; Hannah, Daniel C. Chemical Reviews, Vol. 117, Issue 5 https://doi.org/10.1021/acs.chemrev.6b00614	journal	February 2017
Achievements, Challenges, and Prospects of Calcium Batteries Arroyo-de Dompablo, M. Elena; Ponrouch, Alexandre; Johansson, Patrik Chemical Reviews https://doi.org/10.1021/acs.chemrev.9b00339	journal	October 2019
Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2 Liu, Jue; Yu, Lei; Hu, Enyuan Inorganic Chemistry, Vol. 57, Issue 12 https://doi.org/10.1021/acs.inorgchem.8b00461	journal	May 2018
Electrochemical Reduction of a Spinel-Type Manganese Oxide Cathode in Aqueous Electrolytes with Ca ²⁺ or Zn ²⁺ Nolis, Gene M.; Adil, Abdullah; Yoo, Hyun Deog The Journal of Physical Chemistry C, Vol. 122, Issue 8 https://doi.org/10.1021/acs.jpcc.7b12084	journal	February 2018
Role of Structural H ₂ O in Intercalation Electrodes: The Case of Mg in Nanocrystalline Xerogel-V ₂ O ₅ Sai Gautam, Gopalakrishnan; Canepa, Pieremanuele; Richards, William Davidson Nano Letters, Vol. 16, Issue 4 https://doi.org/10.1021/acs.nanolett.5b05273	journal	March 2016
Water-Activated VOPO ₄ for Magnesium Ion Batteries Ji, Xiao; Chen, Ji; Wang, Fei Nano Letters, Vol. 18, Issue 10 https://doi.org/10.1021/acs.nanolett.8b02854	journal	September 2018
High Capacity for Mg ²⁺ Deintercalation in Spinel Vanadium Oxide Nanocrystals Hu, Linhua; Jokisaari, Jacob R.; Kwon, Bob Jin ACS Energy Letters, Vol. 5, Issue 8 https://doi.org/10.1021/acsenergylett.0c01189	journal	July 2020
High-Voltage Phosphate Cathodes for Rechargeable Ca-Ion Batteries Kim, Sanghyeon; Yin, Liang; Lee, Myeong Hwan ACS Energy Letters, Vol. 5, Issue 10 https://doi.org/10.1021/acsenergylett.0c01663	journal	September 2020
Layered TiS ₂ Positive Electrode for Mg Batteries Sun, Xiaoqi; Bonnick, Patrick; Nazar, Linda F. ACS Energy Letters, Vol. 1, Issue 1 https://doi.org/10.1021/acsenergylett.6b00145	journal	June 2016
Bilayered Mg _0.25 V ₂ O ₅ ·H ₂ O as a Stable Cathode for Rechargeable Ca-Ion Batteries Xu, Xiaoming; Duan, Manyi; Yue, Yunfan ACS Energy Letters, Vol. 4, Issue 6 https://doi.org/10.1021/acsenergylett.9b00830	journal	May 2019
Synthesis of Todorokite at Atmospheric Pressure Feng, Xiong Han; Tan, Wen Feng; Liu, Fan Chemistry of Materials, Vol. 16, Issue 22 https://doi.org/10.1021/cm0499545	journal	November 2004
Role of Electronic Structure in the Susceptibility of Metastable Transition-Metal Oxide Structures to Transformation Reed, John; Ceder, Gerbrand Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020733x	journal	October 2004
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
Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems Martin-Diaconescu, Vlad; Gennari, Marcello; Gerey, Bertrand Inorganic Chemistry, Vol. 54, Issue 4 https://doi.org/10.1021/ic501991e	journal	December 2014
Thermodynamics of Phase Selection in MnO ₂ Framework Structures through Alkali Intercalation and Hydration Kitchaev, Daniil A.; Dacek, Stephen T.; Sun, Wenhao Journal of the American Chemical Society, Vol. 139, Issue 7 https://doi.org/10.1021/jacs.6b11301	journal	February 2017
Revealing and Rationalizing the Rich Polytypism of Todorokite MnO ₂ Hu, Xiaobing; Kitchaev, Daniil A.; Wu, Lijun Journal of the American Chemical Society, Vol. 140, Issue 22 https://doi.org/10.1021/jacs.8b02971	journal	April 2018
Redox Cycling Driven Transformation of Layered Manganese Oxides to Tunnel Structures Jung, Haesung; Taillefert, Martial; Sun, Jingying Journal of the American Chemical Society, Vol. 142, Issue 5 https://doi.org/10.1021/jacs.9b12266	journal	January 2020
Ca L ₂₃ Spectrum in Amorphous and Crystalline Phases of Calcium Carbonate Rez, Peter; Blackwell, Alexander The Journal of Physical Chemistry B, Vol. 115, Issue 38 https://doi.org/10.1021/jp203057y	journal	September 2011
Towards a calcium-based rechargeable battery Ponrouch, A.; Frontera, C.; Bardé, F. Nature Materials, Vol. 15, Issue 2 https://doi.org/10.1038/nmat4462	journal	October 2015
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
In quest of cathode materials for Ca ion batteries: the CaMO ₃ perovskites (M = Mo, Cr, Mn, Fe, Co, and Ni) Arroyo-de Dompablo, M. E.; Krich, C.; Nava-Avendaño, J. Physical Chemistry Chemical Physics, Vol. 18, Issue 29 https://doi.org/10.1039/C6CP03381D	journal	January 2016
Tailoring the electrochemical activity of magnesium chromium oxide towards Mg batteries through control of size and crystal structure Hu, Linhua; Johnson, Ian D.; Kim, Soojeong Nanoscale, Vol. 11, Issue 2 https://doi.org/10.1039/C8NR08347A	journal	January 2019
Towards stable and efficient electrolytes for room-temperature rechargeable calcium batteries Li, Zhenyou; Fuhr, Olaf; Fichtner, Maximilian Energy & Environmental Science, Vol. 12, Issue 12 https://doi.org/10.1039/C9EE01699F	journal	January 2019
Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane Birkner, Nancy; Navrotsky, Alexandra Proceedings of the National Academy of Sciences, Vol. 114, Issue 7 https://doi.org/10.1073/pnas.1620427114	journal	January 2017
Energetics of MnO 2 polymorphs in density functional theory Kitchaev, Daniil A.; Peng, Haowei; Liu, Yun Physical Review B, Vol. 93, Issue 4 https://doi.org/10.1103/PhysRevB.93.045132	journal	January 2016
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
Short-range and long-range order of phyllomanganate nanoparticles determined using high-energy X-ray scattering Manceau, Alain; Marcus, Matthew A.; Grangeon, S. Journal of Applied Crystallography, Vol. 46, Issue 1 https://doi.org/10.1107/S0021889812047917	journal	January 2013
The structure and crystal chemistry of vernadite in ferromanganese crusts Lee, Seungyeol; Xu, Huifang; Xu, Wenqian Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 75, Issue 4 https://doi.org/10.1107/S2052520619006528	journal	June 2019
Todorokites: A New Family of Naturally Occurring Manganese Oxides Turner, S.; Buseck, P. R. Science, Vol. 212, Issue 4498 https://doi.org/10.1126/science.212.4498.1024	journal	May 1981
Steps Towards the Use of TiS ₂ Electrodes in Ca Batteries Verrelli, R.; Black, A.; Dugas, R. Journal of The Electrochemical Society, Vol. 167, Issue 7 https://doi.org/10.1149/1945-7111/ab7a82	journal	January 2020
Cryptomelane formation from nanocrystalline vernadite precursor: a high energy X-ray scattering and transmission electron microscopy perspective on reaction mechanisms Grangeon, Sylvain; Fernandez-Martinez, Alejandro; Warmont, Fabienne Geochemical Transactions, Vol. 16, Issue 1 https://doi.org/10.1186/s12932-015-0028-y	journal	September 2015
Birnessite polytype systematics and identification by powder X-ray diffraction Drits, V. A.; Lanson, B.; Gaillot, A. -C. American Mineralogist, Vol. 92, Issue 5-6 https://doi.org/10.2138/am.2007.2207	journal	May 2007
Layered Metal Hydroxides Containing Calcium and Their Structural Analysis Kim, Tae-Hyun; Heo, Il; Paek, Seung-Min Bulletin of the Korean Chemical Society, Vol. 33, Issue 6 https://doi.org/10.5012/bkcs.2012.33.6.1845	journal	June 2012

Similar Records

Intercalation of Mg into a Few-Layer Phyllomanganate in Non-aqueous Electrolytes at Room Temperature

Journal Article · 2020 · Chemistry of Materials · OSTI ID:1659764

Kwon, Bob Jin; Kim, Chunjoong; Jokisaari, Jacob R.; +9 more

Impact of Stabilizing Cations on Lithium Intercalation in Tunneled Manganese Oxide Cathodes

Journal Article · 2021 · ACS Applied Energy Materials · OSTI ID:1923077

Kempaiah, Ravindra; Chan, Henry; Srinivasan, Srilok; +3 more

Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

Journal Article · 2022 · Nature Sustainability · OSTI ID:1900589

Yuan, Yifei; Sharpe, Ryan; He, Kun; +11 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemical structure
electrodes
intercalation
oxides
transition metals

Title: Intercalation of Ca into a Highly Defective Manganese Oxide at Room Temperature

Citation Formats

References (53)

Similar Records

Related Subjects