Nonstoichiometry and Defects in Hydrothermally Synthesized ε-LiVOPO 4

Chung, Youngmin; Cassidy, Ellen; Lee, Krystal; Siu, Carrie; Huang, Yiqing; Omenya, Fredrick; Rana, Jatinkumar; Wiaderek, Kamila M.; Chernova, Natasha A.; Chapman, Karena W.; Piper, Louis F.  J.; Whittingham, M. Stanley

doi:10.1021/acsaem.9b00448

Title: Nonstoichiometry and Defects in Hydrothermally Synthesized ε-LiVOPO ₄

Journal Article · Fri Jun 07 00:00:00 EDT 2019 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.9b00448· OSTI ID:1767481

^[1]; Cassidy, Ellen ^[2]; Lee, Krystal ^[2]; Siu, Carrie ^[2]; Huang, Yiqing ^[1]; Omenya, Fredrick ^[3];

^[2]; Wiaderek, Kamila M. ^[4];

^[1];

^[4];

^[2];

^[1]

Binghamton Univ., NY (United States). NorthEast Center for Chemical Energy Storage; Binghamton Univ., NY (United States)
Binghamton Univ., NY (United States). NorthEast Center for Chemical Energy Storage
Binghamton Univ., NY (United States)
Binghamton Univ., NY (United States). NorthEast Center for Chemical Energy Storage; Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

ε-LiVOPO₄ has been synthesized through the hydrothermal method by adjusting the pH of the hydrothermal solution and the reaction temperature. This phase is formed between 180 and 220 °C, as diamond-like crystals around 10–15 μm in size. X-ray diffraction (XRD) analysis shows that hydrothermal ε-LiVOPO₄ lattice parameters a and b linearly decrease, while c linearly increases when the synthesis temperature increases. Thermogravimetric analysis with mass spectroscopy reveals 1.5 to 0.5% water loss at about 350 °C for ε-LiVOPO₄ synthesized at 180 and 220 °C, suggesting water or protons incorporation into the structure. Magnetic studies reveal ferrimagnetism in hydrothermal ε-LiVOPO₄ below 10 K, as opposed to antiferromagnetic ordering below 14 K found in samples synthesized at high temperature. In-situ XRD upon heating of the hydrothermal ε-LiVOPO₄ synthesized at 180, 200, and 220 °C reveals that the temperature dependences of their lattice parameters merge at about 500 °C; furthermore, at the same temperature the structure reversibly changes from triclinic to monoclinic. The lattice parameters and the magnetic properties of the hydrothermal samples heated to 750 °C are similar to those of solid-state synthesized ε-LiVOPO₄. Based on structure and composition analysis, we suggest that hydrothermal samples can be described as an ε-Li_1+xH_yV_1–zOPO₄ (x, y, z < 0.1) solid solution. The electrochemical characterization of hydrothermal ε-LiVOPO₄ reveals the first cycle capacity of about 300 mAh/g, which holds for about five cycles, gradually decreasing thereafter. The low-voltage region does not reveal voltage plateaus corresponding to Li_1.5VOPO₄ and Li_1.75VOPO₄ phases found in the solid-state material, further suggesting structural disorder in the low-temperature samples evidenced from the lattice parameters and the magnetic properties.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); State Univ. of New York (SUNY), Albany, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: SC0001294; SC0012583; AC02-06CH11357

OSTI ID:: 1767481

Alternate ID(s):: OSTI ID: 1774618

Journal Information:: ACS Applied Energy Materials, Vol. 2, Issue 7; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (34)

Hollow α-LiVOPO4 sphere cathodes for high energy Li-ion battery application Saravanan, Kuppan; Lee, Hwang Sheng; Kuezma, Mirjana Journal of Materials Chemistry, Vol. 21, Issue 27 https://doi.org/10.1039/c0jm04428h	journal	January 2011
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Nanostructured Li ₂ MnSiO ₄ /C Cathodes with Hierarchical Macro-/Mesoporosity for Lithium-Ion Batteries He, Guang; Manthiram, Arumugam Advanced Functional Materials, Vol. 24, Issue 33 https://doi.org/10.1002/adfm.201400610	journal	June 2014
Synthesis and electrochemical studies of layer-structured metastable αI-LiVOPO4 Shahul Hameed, A.; Nagarathinam, Mangayarkarasi; Reddy, M. V. Journal of Materials Chemistry, Vol. 22, Issue 15 https://doi.org/10.1039/c2jm00062h	journal	January 2012
Phosphates as Lithium-Ion Battery Cathodes: An Evaluation Based on High-Throughput ab Initio Calculations Hautier, Geoffroy; Jain, Anubhav; Ong, Shyue Ping Chemistry of Materials, Vol. 23, Issue 15 https://doi.org/10.1021/cm200949v	journal	August 2011
LiMn _0.8 Fe _0.2 PO ₄ : An Advanced Cathode Material for Rechargeable Lithium Batteries Martha, Surendra K.; Grinblat, Judith; Haik, Ortal Angewandte Chemie International Edition, Vol. 48, Issue 45 https://doi.org/10.1002/anie.200903587	journal	October 2009
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
Multiple phases in the ε-VPO ₄ O–LiVPO ₄ O–Li ₂ VPO ₄ O system: a combined solid state electrochemistry and diffraction structural study Bianchini, M.; Ateba-Mba, J. M.; Dagault, P. J. Mater. Chem. A, Vol. 2, Issue 26 https://doi.org/10.1039/C4TA01518E	journal	January 2014
Thermodynamics, Kinetics and Structural Evolution of ε-LiVOPO ₄ over Multiple Lithium Intercalation Lin, Yuh-Chieh; Wen, Bohua; Wiaderek, Kamila M. Chemistry of Materials, Vol. 28, Issue 6 https://doi.org/10.1021/acs.chemmater.5b04880	journal	February 2016
Microwave-Assisted Solvothermal Synthesis and Characterization of Various Polymorphs of LiVOPO ₄ Harrison, Katharine L.; Manthiram, Arumugam Chemistry of Materials, Vol. 25, Issue 9 https://doi.org/10.1021/cm400227j	journal	April 2013
Enabling multi-electron reaction of ε-VOPO ₄ to reach theoretical capacity for lithium-ion batteries Siu, Carrie; Seymour, Ieuan D.; Britto, Sylvia Chemical Communications, Vol. 54, Issue 56 https://doi.org/10.1039/C8CC02386G	journal	January 2018
The hydrothermal synthesis and characterization of olivines and related compounds for electrochemical applications Chen, Jiajun; Vacchio, Michael J.; Wang, Shijun Solid State Ionics, Vol. 178, Issue 31-32 https://doi.org/10.1016/j.ssi.2007.10.015	journal	January 2008
Role of disorder in limiting the true multi-electron redox in ε-LiVOPO ₄ Rana, Jatinkumar; Shi, Yong; Zuba, Mateusz J. Journal of Materials Chemistry A, Vol. 6, Issue 42 https://doi.org/10.1039/C8TA06469E	journal	January 2018
Electrochemical Performance of Nanosized Disordered LiVOPO ₄ Shi, Yong; Zhou, Hui; Seymour, Ieuan D. ACS Omega, Vol. 3, Issue 7 https://doi.org/10.1021/acsomega.8b00763	journal	July 2018
Olivine LiCoPO[sub 4] as 4.8 V Electrode Material for Lithium Batteries Amine, K. Electrochemical and Solid-State Letters, Vol. 3, Issue 4 https://doi.org/10.1149/1.1390994	journal	January 1999
Synthesis, Structure and Electrochemistry of Lithium Vanadium Phosphate Cathode Materials Allen, Chris J.; Jia, Qinging; Chinnasamy, C. N. Journal of The Electrochemical Society, Vol. 158, Issue 12 https://doi.org/10.1149/2.003112jes	journal	January 2011
Microwave-Solvothermal Synthesis of Nanostructured Li ₂ MSiO ₄ /C (M = Mn and Fe) Cathodes for Lithium-Ion Batteries Muraliganth, T.; Stroukoff, K. R.; Manthiram, A. Chemistry of Materials, Vol. 22, Issue 20 https://doi.org/10.1021/cm102058n	journal	October 2010
Enhancing the performances of Li-ion batteries by carbon-coating: present and future Li, Huiqiao; Zhou, Haoshen Chem. Commun., Vol. 48, Issue 9 https://doi.org/10.1039/C1CC14764A	journal	January 2012
Electrochemical Properties of Beta-LiVOPO[sub 4] Prepared by Carbothermal Reduction Barker, J.; Saidi, M. Y.; Swoyer, J. L. Journal of The Electrochemical Society, Vol. 151, Issue 6 https://doi.org/10.1149/1.1723494	journal	January 2004
ε-VOPO[sub 4]: Electrochemical Synthesis and Enhanced Cathode Behavior Song, Yanning; Zavalij, Peter Y.; Whittingham, M. Stanley Journal of The Electrochemical Society, Vol. 152, Issue 4 https://doi.org/10.1149/1.1862265	journal	January 2005
Synthesis and Crystallographic Study of Homeotypic LiVPO ₄ F and LiVPO ₄ O Ateba Mba, Jean-Marcel; Masquelier, Christian; Suard, Emmanuelle Chemistry of Materials, Vol. 24, Issue 6 https://doi.org/10.1021/cm3003996	journal	February 2012
Some transition metal (oxy)phosphates and vanadium oxides for lithium batteries Whittingham, M. Stanley; Song, Yanning; Lutta, Samuel Journal of Materials Chemistry, Vol. 15, Issue 33 https://doi.org/10.1039/b501961c	journal	January 2005
Crystal Chemistry of the Olivine-Type Li(Mn[sub y]Fe[sub 1−y])PO[sub 4] and (Mn[sub y]Fe[sub 1−y])PO[sub 4] as Possible 4 V Cathode Materials for Lithium Batteries Yamada, Atsuo; Chung, Sai-Cheong Journal of The Electrochemical Society, Vol. 148, Issue 8 https://doi.org/10.1149/1.1385377	journal	January 2001
LiMnPO[sub 4] as the Cathode for Lithium Batteries Li, Guohua; Azuma, Hideto; Tohda, Masayuki Electrochemical and Solid-State Letters, Vol. 5, Issue 6 https://doi.org/10.1149/1.1475195	journal	January 2002
Electrochemical Behavior of Nanostructured ɛ-VOPO₄ over Two Redox Plateaus Chen, Z.; Chen, Q.; Chen, L. Journal of the Electrochemical Society, Vol. 160, Issue 10, p. A1777-A1780 https://doi.org/10.1149/2.064310jes	journal	January 2013
History, Evolution, and Future Status of Energy Storage Whittingham, M. S. Proceedings of the IEEE, Vol. 100, Issue Special Centennial Issue https://doi.org/10.1109/JPROC.2012.2190170	journal	May 2012
Li/β-VOPO[sub 4]: A New 4 V System for Lithium Batteries Gaubicher, J. Journal of The Electrochemical Society, Vol. 146, Issue 12 https://doi.org/10.1149/1.1392646	journal	January 1999
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
Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries Padhi, A. K. Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194 https://doi.org/10.1149/1.1837571	journal	April 1997
Highly Reversible Li Insertion at 4 V in ɛ-VOPO[sub 4]/α-LiVOPO[sub 4] Cathodes Kerr, T. A. Electrochemical and Solid-State Letters, Vol. 3, Issue 10 https://doi.org/10.1149/1.1391179	journal	January 1999
Redox transformations of simple vanadium phosphates: the synthesis of ε-VOPO4 Lim, S. Solid State Ionics, Vol. 84, Issue 3-4 https://doi.org/10.1016/0167-2738(96)00007-0	journal	April 1996
Towards the understanding of poor electrochemical activity of triclinic LiVOPO4: Experimental characterization and theoretical investigations Yang, Yong; Fang, Haisheng; Zheng, Jing Solid State Sciences, Vol. 10, Issue 10 https://doi.org/10.1016/j.solidstatesciences.2008.01.028	journal	October 2008
Structural and Electrochemical Properties of Li ₂ Mn _0.5 Fe _0.5 SiO ₄ /C Cathode Nanocomposite Chung, Young-Min; Yu, Seung-Ho; Song, Min-Seob Bulletin of the Korean Chemical Society, Vol. 32, Issue 12 https://doi.org/10.5012/bkcs.2011.32.12.4205	journal	December 2011
A novel sol–gel method to synthesize nanocrystalline LiVPO4F and its electrochemical Li intercalation performances Li, Yuzhan; Zhou, Zhen; Gao, X. P. Journal of Power Sources, Vol. 160, Issue 1 https://doi.org/10.1016/j.jpowsour.2006.01.067	journal	September 2006

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25 ENERGY STORAGE
energy storage (including batteries and capacitors)
defects
charge transport
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cathode
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Title: Nonstoichiometry and Defects in Hydrothermally Synthesized ε-LiVOPO 4

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Title: Nonstoichiometry and Defects in Hydrothermally Synthesized ε-LiVOPO ₄