Doctoral Dissertations


”Through this investigation polyanion-based cathode materials including sulfates, phosphates, and phosphites of transition metal have been synthesized for lithium and sodium-ion batteries and their electrochemical performances were evaluated. The emphasis was on soft chemical routes to discover metastable phases which are often missed in high temperature synthesis. Iron-based compounds were the main focus of this investigation, however, concurrently a few vanadium-analogues of iron compounds were investigated to evaluate the effect of multi-electron process on achievable voltage and capacity.

This investigation resulted in the discovery of several compounds with unique crystal structures, namely AFe3(SO4)2(OH)6 (A = Na/NH4), NaFe(HPO4)2, Li2Fe(H0.5PO4)2, Li3Fe(PO4)2, Fe3(PO4)2(OH)2, LiV(HPO3)2 and Na3(VO)2(PO4)2F. Single-crystal and synchrotron powder X-ray diffraction techniques have been used to determine the crystal structures. Partial fluoro-substitution in NaFe3(SO4)2(OH)6 improved Li-ion insertion voltage and achievable capacity owing to a synergistic effect of smaller particle size and inductive effect. A new composition, NaFe(HPO4)2, was synthesized through a hydrothermal route. Subsequent partial and full ion-exchange produced two new electroactive compounds, Li2Fe(H0.5PO4)2 and Li3Fe(PO4)2, respectively. A mineral, barbosalite, Fe3(PO4)2(OH)2, has been evaluated as a cathode for Li-ion battery and exhibited capacity enhancement on cycling. LiV(HPO3)2 and Na3(VO)2(PO4)2F exhibited facile electrochemistry with an average voltage of 4.0 and 3.8 V in Li- and Na-ion batteries, respectively. Both of these compounds showed two electron processes with capacities exceeding 125 and 150 mAh.g-1, respectively"--Abstract, page iv.


Choudhury, Amitava

Committee Member(s)

Whitefield, Philip D.
Nath, Manashi
Switzer, Jay A., 1950-
Liang, Xinhua



Degree Name

Ph. D. in Chemistry


The authors acknowledge the funding from Energy Research and Development Center (Missouri S&T) and University of Missouri Research Board.


Missouri University of Science and Technology

Publication Date

Spring 2020

Journal article titles appearing in thesis/dissertation

  • Kagomé lattices as cathode: Effect of particle size and fluoride substitution on electrochemical lithium insertion in sodium- and ammonium jarosites
  • Soft chemical routes to new iron phosphates and their electrochemical properties
  • Electrochemistry of illusive barbosalite, Fe²⁺Fe³⁺ ₂(PO₄)₂(OH)₂: An iron phosphate related to lipscombite structure
  • A square channel vanadium phosphite framework as high voltage cathode for Li- and Na- ion batteries
  • Na3V2O2(PO4)2F as a high voltage cathode for Na- and Li-ion batteries


xx, 236 pages

Note about bibliography

Includes bibliographic references.


© 2020 Prashanth Sandineni, All rights reserved.

Document Type

Dissertation - Open Access

File Type




Thesis Number

T 11886

Electronic OCLC #


Included in

Chemistry Commons