Calorimetric Study of Mixed Phosphates Na4M3(PO4)2P2O7 (M = Mn2+, Fe2+, Co2+, Ni2+) to Evaluate the Electrochemical Trends

Jayanthi, K.; Lochab, Shubham; Barpanda, Prabeer; Navrotsky, Alexandra

doi:10.1021/acs.jpcc.3c01975

Calorimetric Study of Mixed Phosphates Na₄M₃(PO₄)₂P₂O₇ (M = Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺) to Evaluate the Electrochemical Trends

Journal Article · Mon Jun 12 04:00:00 EDT 2023 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.3c01975· OSTI ID:1987773

^[1]; Lochab, Shubham ^[2]; ^[3]; ^[4]

Arizona State University, Tempe, AZ (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Indian Institute of Science, Bangalore (India). Faraday Materials Laboratory
Indian Institute of Science, Bangalore (India). Faraday Materials Laboratory; Helmholtz Institute Ulm (Germany); Karlsruhe Institute of Technology (KIT) (Germany)
Arizona State University, Tempe, AZ (United States)

Mixed polyanionic compounds have been studied extensively as viable cathode materials for sodium-ion batteries. Mixed phosphates, Na₄M₃(PO₄)₂P₂O₇ (M = Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺), provide a low barrier for Na-ion diffusion, being advantageous in comparison to phosphates and pyrophosphates. The reported order of sodium extraction is ambiguous and remains unclear. Despite being structurally similar, electrochemical performance differs for all four analogues with different degrees of (de)sodiation, according to the transition element present. High-temperature oxide melt solution calorimetry has been used to establish the relation between thermodynamic phase stability and observed capacity for this series of mixed phosphates. Thermodynamic phase stability largely depends on the kind of structure, type of bonding, and size of the cations present. So, according to our results, the thermodynamic phase stability follows the order Na₄Mn₃(PO₄)₂P₂O₇ > Na₄Fe₃(PO₄)₂P₂O₇ > Na₄Co₃(PO₄)₂P₂O₇ > Na₄Ni₃(PO₄)₂P₂O₇. The thermodynamic studies serve as guidelines for the selection of compositions with the potential for fabricating advanced cathode materials with maximum performance.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Government of India; Alexander von Humboldt Foundation

Grant/Contract Number:: AC05-00OR22725; SC0021987

OSTI ID:: 1987773

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 24 Vol. 127; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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