Abstract
The transport properties and lithium insertion mechanism into the first mixed valence silver-copper oxide AgCuO2 and the B-site mixed magnetic delafossite AgCu0.5Mn0.5O2 were investigated by means of four probes DC measurements combined with thermopower measurements and in situ XRD investigations. AgCuO2 and AgCu0.5Mn0.5O2 display p-type conductivity with Seebeck coefficient of Q=+2.46 and +78.83 μV/K and conductivity values of σ=3.2×10-1 and 1.8×10-4 S/cm, respectively. The high conductivity together with the low Seebeck coefficient of AgCuO2 is explained as a result of the mixed valence state between Ag and Cu sites. The electrochemically assisted lithium insertion into AgCuO2 shows a solid solution domain between x=0 and 0.8Li+ followed by a plateau nearby 1.7 V (vs. Li+/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 AgCu0.5Mn0.5O2 also exhibits Li+/Ag+ displacement reaction in a comparable potential range than AgCuO2; however, with a prior narrow solid solution domain and a less rapid amorphization process. AgCuO2 and AgCu0.5Mn0.5O2 provide a discharge gravimetric capacity of 265 and 230 mA h/g above 1.5 V (vs. Li+/Li), respectively, with no evidence of a new defined phases.
| Original language | English |
|---|---|
| Pages (from-to) | 374-380 |
| Number of pages | 7 |
| Journal | Journal of Solid State Chemistry |
| Volume | 182 |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - Feb 2009 |
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Keywords
- Delafossite
- In situ XRD
- Lithium batteries
- p-Type semi-conductors
- Silver-copper mixed oxides
ASJC Scopus subject areas
- Condensed Matter Physics
- Inorganic Chemistry
- Physical and Theoretical Chemistry
- Ceramics and Composites
- Electronic, Optical and Magnetic Materials
- Materials Chemistry
Cite this
Transport properties and lithium insertion study in the p-type semi-conductors AgCuO2 and AgCu0.5Mn0.5O2. / Sauvage, F.; Muñoz-Rojas, D.; Poeppelmeier, Kenneth R; Casañ-Pastor, N.
In: Journal of Solid State Chemistry, Vol. 182, No. 2, 02.2009, p. 374-380.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Transport properties and lithium insertion study in the p-type semi-conductors AgCuO2 and AgCu0.5Mn0.5O2
AU - Sauvage, F.
AU - Muñoz-Rojas, D.
AU - Poeppelmeier, Kenneth R
AU - Casañ-Pastor, N.
PY - 2009/2
Y1 - 2009/2
N2 - The transport properties and lithium insertion mechanism into the first mixed valence silver-copper oxide AgCuO2 and the B-site mixed magnetic delafossite AgCu0.5Mn0.5O2 were investigated by means of four probes DC measurements combined with thermopower measurements and in situ XRD investigations. AgCuO2 and AgCu0.5Mn0.5O2 display p-type conductivity with Seebeck coefficient of Q=+2.46 and +78.83 μV/K and conductivity values of σ=3.2×10-1 and 1.8×10-4 S/cm, respectively. The high conductivity together with the low Seebeck coefficient of AgCuO2 is explained as a result of the mixed valence state between Ag and Cu sites. The electrochemically assisted lithium insertion into AgCuO2 shows a solid solution domain between x=0 and 0.8Li+ followed by a plateau nearby 1.7 V (vs. Li+/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 AgCu0.5Mn0.5O2 also exhibits Li+/Ag+ displacement reaction in a comparable potential range than AgCuO2; however, with a prior narrow solid solution domain and a less rapid amorphization process. AgCuO2 and AgCu0.5Mn0.5O2 provide a discharge gravimetric capacity of 265 and 230 mA h/g above 1.5 V (vs. Li+/Li), respectively, with no evidence of a new defined phases.
AB - The transport properties and lithium insertion mechanism into the first mixed valence silver-copper oxide AgCuO2 and the B-site mixed magnetic delafossite AgCu0.5Mn0.5O2 were investigated by means of four probes DC measurements combined with thermopower measurements and in situ XRD investigations. AgCuO2 and AgCu0.5Mn0.5O2 display p-type conductivity with Seebeck coefficient of Q=+2.46 and +78.83 μV/K and conductivity values of σ=3.2×10-1 and 1.8×10-4 S/cm, respectively. The high conductivity together with the low Seebeck coefficient of AgCuO2 is explained as a result of the mixed valence state between Ag and Cu sites. The electrochemically assisted lithium insertion into AgCuO2 shows a solid solution domain between x=0 and 0.8Li+ followed by a plateau nearby 1.7 V (vs. Li+/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 AgCu0.5Mn0.5O2 also exhibits Li+/Ag+ displacement reaction in a comparable potential range than AgCuO2; however, with a prior narrow solid solution domain and a less rapid amorphization process. AgCuO2 and AgCu0.5Mn0.5O2 provide a discharge gravimetric capacity of 265 and 230 mA h/g above 1.5 V (vs. Li+/Li), respectively, with no evidence of a new defined phases.
KW - Delafossite
KW - In situ XRD
KW - Lithium batteries
KW - p-Type semi-conductors
KW - Silver-copper mixed oxides
UR - http://www.scopus.com/inward/record.url?scp=58549083106&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=58549083106&partnerID=8YFLogxK
U2 - 10.1016/j.jssc.2008.10.038
DO - 10.1016/j.jssc.2008.10.038
M3 - Article
AN - SCOPUS:58549083106
VL - 182
SP - 374
EP - 380
JO - Journal of Solid State Chemistry
JF - Journal of Solid State Chemistry
SN - 0022-4596
IS - 2
ER -