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Title: Transport properties and lithium insertion study in the p-type semi-conductors AgCuO{sub 2} and AgCu{sub 0.5}Mn{sub 0.5}O{sub 2}

Abstract

The transport properties and lithium insertion mechanism into the first mixed valence silver-copper oxide AgCuO{sub 2} and the B-site mixed magnetic delafossite AgCu{sub 0.5}Mn{sub 0.5}O{sub 2} were investigated by means of four probes DC measurements combined with thermopower measurements and in situ XRD investigations. AgCuO{sub 2} and AgCu{sub 0.5}Mn{sub 0.5}O{sub 2} display p-type conductivity with Seebeck coefficient of Q=+2.46 and +78.83 {mu}V/K and conductivity values of {sigma}=3.2x10{sup -1} and 1.8x10{sup -4} S/cm, respectively. The high conductivity together with the low Seebeck coefficient of AgCuO{sub 2} is explained as a result of the mixed valence state between Ag and Cu sites. The electrochemically assisted lithium insertion into AgCuO{sub 2} shows a solid solution domain between x=0 and 0.8Li{sup +} followed by a plateau nearby 1.7 V (vs. Li{sup +}/Li) entailing the reduction of silver to silver metal accordingly to a displacement reaction. During the solid solution, a rapid structure amorphization was observed. The delafossite AgCu{sub 0.5}Mn{sub 0.5}O{sub 2} also exhibits Li{sup +}/Ag{sup +} displacement reaction in a comparable potential range than AgCuO{sub 2}; however, with a prior narrow solid solution domain and a less rapid amorphization process. AgCuO{sub 2} and AgCu{sub 0.5}Mn{sub 0.5}O{sub 2} provide a discharge gravimetric capacity of 265more » and 230 mA h/g above 1.5 V (vs. Li{sup +}/Li), respectively, with no evidence of a new defined phases. - Graphical abstract: Investigation on the transport properties of AgCuO{sub 2} and the new B-site mixed Delafossite AgCu{sub 0.5}Mn{sub 0.5}O{sub 2} shows a p-type conductivity of {sigma}=3.2x10{sup -1} and 1.8x10{sup -4} S/cm, respectively. The high conductivity, as a result from a high charge carrier density in AgCuO{sub 2} supports the existence of a mixed valence state between silver and copper. A particular emphasis is also placed on the electrochemical lithium insertion properties into these two materials by in situ XRD measurements to better insight on the Li{sup +} insertion mechanism and also scrutinize possible new compounds electrochemically accessible in the Li-Ag-Cu system.« less

Authors:
 [1];  [2]
  1. Department of Chemistry and Materials Research Center, Northwestern University, Evanston, IL 60208-3113 (United States)
  2. Instituto de Ciencia de Materiales de Barcelona, CSIC, Campus UAB, 08193 Bellaterra, Barcelona (Spain)
Publication Date:
OSTI Identifier:
21212202
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 182; Journal Issue: 2; Other Information: DOI: 10.1016/j.jssc.2008.10.038; PII: S0022-4596(08)00526-4; Copyright (c) 2008 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMORPHOUS STATE; CHARGE CARRIERS; COPPER OXIDES; ELECTROCHEMISTRY; LITHIUM; LITHIUM IONS; MANGANESE OXIDES; SILVER IONS; SILVER OXIDES; X-RAY DIFFRACTION

Citation Formats

Sauvage, F., Munoz-Rojas, D., Poeppelmeier, K R, and Casan-Pastor, N. Transport properties and lithium insertion study in the p-type semi-conductors AgCuO{sub 2} and AgCu{sub 0.5}Mn{sub 0.5}O{sub 2}. United States: N. p., 2009. Web. doi:10.1016/j.jssc.2008.10.038.
Sauvage, F., Munoz-Rojas, D., Poeppelmeier, K R, & Casan-Pastor, N. Transport properties and lithium insertion study in the p-type semi-conductors AgCuO{sub 2} and AgCu{sub 0.5}Mn{sub 0.5}O{sub 2}. United States. https://doi.org/10.1016/j.jssc.2008.10.038
Sauvage, F., Munoz-Rojas, D., Poeppelmeier, K R, and Casan-Pastor, N. 2009. "Transport properties and lithium insertion study in the p-type semi-conductors AgCuO{sub 2} and AgCu{sub 0.5}Mn{sub 0.5}O{sub 2}". United States. https://doi.org/10.1016/j.jssc.2008.10.038.
@article{osti_21212202,
title = {Transport properties and lithium insertion study in the p-type semi-conductors AgCuO{sub 2} and AgCu{sub 0.5}Mn{sub 0.5}O{sub 2}},
author = {Sauvage, F. and Munoz-Rojas, D. and Poeppelmeier, K R and Casan-Pastor, N},
abstractNote = {The transport properties and lithium insertion mechanism into the first mixed valence silver-copper oxide AgCuO{sub 2} and the B-site mixed magnetic delafossite AgCu{sub 0.5}Mn{sub 0.5}O{sub 2} were investigated by means of four probes DC measurements combined with thermopower measurements and in situ XRD investigations. AgCuO{sub 2} and AgCu{sub 0.5}Mn{sub 0.5}O{sub 2} display p-type conductivity with Seebeck coefficient of Q=+2.46 and +78.83 {mu}V/K and conductivity values of {sigma}=3.2x10{sup -1} and 1.8x10{sup -4} S/cm, respectively. The high conductivity together with the low Seebeck coefficient of AgCuO{sub 2} is explained as a result of the mixed valence state between Ag and Cu sites. The electrochemically assisted lithium insertion into AgCuO{sub 2} shows a solid solution domain between x=0 and 0.8Li{sup +} followed by a plateau nearby 1.7 V (vs. Li{sup +}/Li) entailing the reduction of silver to silver metal accordingly to a displacement reaction. During the solid solution, a rapid structure amorphization was observed. The delafossite AgCu{sub 0.5}Mn{sub 0.5}O{sub 2} also exhibits Li{sup +}/Ag{sup +} displacement reaction in a comparable potential range than AgCuO{sub 2}; however, with a prior narrow solid solution domain and a less rapid amorphization process. AgCuO{sub 2} and AgCu{sub 0.5}Mn{sub 0.5}O{sub 2} provide a discharge gravimetric capacity of 265 and 230 mA h/g above 1.5 V (vs. Li{sup +}/Li), respectively, with no evidence of a new defined phases. - Graphical abstract: Investigation on the transport properties of AgCuO{sub 2} and the new B-site mixed Delafossite AgCu{sub 0.5}Mn{sub 0.5}O{sub 2} shows a p-type conductivity of {sigma}=3.2x10{sup -1} and 1.8x10{sup -4} S/cm, respectively. The high conductivity, as a result from a high charge carrier density in AgCuO{sub 2} supports the existence of a mixed valence state between silver and copper. A particular emphasis is also placed on the electrochemical lithium insertion properties into these two materials by in situ XRD measurements to better insight on the Li{sup +} insertion mechanism and also scrutinize possible new compounds electrochemically accessible in the Li-Ag-Cu system.},
doi = {10.1016/j.jssc.2008.10.038},
url = {https://www.osti.gov/biblio/21212202}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 2,
volume = 182,
place = {United States},
year = {Sun Feb 15 00:00:00 EST 2009},
month = {Sun Feb 15 00:00:00 EST 2009}
}