Solid state NMR studies of phosphate/tin matrix formed on electrochemical insertion into SnP2O7

PS Attidekou, PA Connor, Philip Wormald, David Prestwich Tunstall, SM Francis, John Thomas Sirr Irvine

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29 Citations (Scopus)

Abstract

Tin pyrophosphate was synthesised and tested as an anode in lithium ion batteries. This material has a very good reversible capacity of 360 mA h g(-1) with good capacity retention. The source of this good cycling behaviour is thought to be related to the phosphate matrix, which we have investigated in this study. The pyrophosphate is irreversibly reduced during the lithium insertion in the first cycle, converting the phosphorus from P-V to P-IV as confirmed by XPS, coulometry and IR. P-31 MAS NMR indicates a single species near in position to that expected for Li3PO4 but this species would be inconsistent with the observed phosphate reduction. Li-6 MAS NMR shows no presence of Li2O. IR exhibits similar bands to pyrophosphate but these are shifted to lower frequency, suggesting a decrease in bond order. Hence, it seems the pyrophosphate linkage retained but the phosphate is reduced, indicating the dominant phosphate species in the matrix is a ((P2O7)-O-IV)(6-) species analogous to disilicate. (C) 2004 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)185-190
Number of pages6
JournalSolid State Ionics
Volume175
DOIs
Publication statusPublished - 30 Nov 2004

Keywords

  • galvanostatic cycling
  • cyclic voltammetry
  • P-31 and Li-6 MAS NMR
  • IR
  • XPS
  • LITHIUM BATTERIES
  • CRYSTALLINE
  • PYROPHOSPHATES
  • SPECTROSCOPY
  • COORDINATION
  • PERFORMANCE
  • SN2P2O7
  • GLASSES
  • ANODES
  • LI-6

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