TY - JOUR
T1 - Experimental Thermodynamic Characterization of the Chalcopyrite-Based Compounds in the Ag–In–Te System for a Potential Thermoelectric Application
AU - Moroz, Mykola
AU - Tesfaye, Fiseha
AU - Demchenko, Pavlo
AU - Mastronardo, Emanuela
AU - Mysina, Oksana
AU - Prokhorenko, Myroslava
AU - Prokhorenko, Serhiy
AU - Lindberg, Daniel
AU - Reshetnyak, Oleksandr
AU - Hupa, Leena
N1 - Funding Information:
This research was supported by the national projects of the Ministry of Education and Science of Ukraine: “Scientific and experimental basis for the production of composite oxide, chalcogenide materials with extended service life” (No. 0121U109620) and “Synthesis, physicochemical and thermodynamic properties of nanosized and nanostructured materials for electrochemical systems” (No. 0120U102184). This work was partly funded by Svenska kulturfonden (Swedish Cultural Foundation in Finland) under the project “Innovative e-waste recycling processes for greener and more efficient recoveries of critical metals and energy” at Åbo Akademi University.
Publisher Copyright:
© 2022 by the authors.
PY - 2022/11
Y1 - 2022/11
N2 - The equilibrium concentration space of the Ag–In–Te system in the part AgInTe2–Te–In2Te3 was studied through the modified solid-state electromotive force (EMF) method by dividing In2Te3–In2Te5–Ag3In97Te147 (I), In2Te5–Te–Ag3In97Te147 (II), Ag3In97Te147–Te–AgIn5Te8 (III), AgIn5Te8–Te–AgIn3Te5 (IV), and AgIn3Te5–Te–AgInTe2 (V), into separate phase regions at T ≤ 500 K. The formation of a thermodynamically stable combination of the binary and ternary phases in the (I)–(V) phase regions from a metastable phase mixture of substances was carried out at T ≤ 500 K in the R(Ag+) part of the positive electrode (PE) of the galvanic cells (GCs) of the structure: (−) C |∙| Ag |∙| SE |∙| R(Ag+) |∙| PE |∙| C (+), where C is the graphite (inert electrode), SE is the solid-state electrolyte (Ag3GeS3Br glass), and Ag is the left (negative) electrode. The Ag+ ions in the R(Ag+) region functioned as small nucleation centers for the formation of the stable phases. The spatial position of the (I)–(V) phase regions in the concentration space of the Ag–In–Te system relative to the position of silver was used to express the overall potential-forming reactions with the participation of the substances Ag, Te, In2Te5, Ag3In97Te147, AgIn5Te8, AgIn3Te5, and AgInTe2. The subsequent EMF measurements were carried out by applying the same GCs. The temperature dependences of the EMF of GCs with PE of the (I)–(V) phase regions were here used to determine, for the first time, the values of standard thermodynamic functions of the binary and ternary compounds. The determined values of the Gibbs energies of the formation of compounds are equal: (Formula presented.), (Formula presented.), (Formula presented.), (Formula presented.), and (Formula presented.) The correctness of the division of the equilibrium phase space of the Ag–In–Te system in the part AgInTe2–Te–In2Te3 involving the AgInTe2, AgIn3Te5, AgIn5Te8, and Ag3In97Te147 compounds was confirmed by the agreement of the calculated and literature-based thermodynamic data for In2Te5 compound. Compositions of pairs of the ternary compounds for their subsequent practical application were proposed.
AB - The equilibrium concentration space of the Ag–In–Te system in the part AgInTe2–Te–In2Te3 was studied through the modified solid-state electromotive force (EMF) method by dividing In2Te3–In2Te5–Ag3In97Te147 (I), In2Te5–Te–Ag3In97Te147 (II), Ag3In97Te147–Te–AgIn5Te8 (III), AgIn5Te8–Te–AgIn3Te5 (IV), and AgIn3Te5–Te–AgInTe2 (V), into separate phase regions at T ≤ 500 K. The formation of a thermodynamically stable combination of the binary and ternary phases in the (I)–(V) phase regions from a metastable phase mixture of substances was carried out at T ≤ 500 K in the R(Ag+) part of the positive electrode (PE) of the galvanic cells (GCs) of the structure: (−) C |∙| Ag |∙| SE |∙| R(Ag+) |∙| PE |∙| C (+), where C is the graphite (inert electrode), SE is the solid-state electrolyte (Ag3GeS3Br glass), and Ag is the left (negative) electrode. The Ag+ ions in the R(Ag+) region functioned as small nucleation centers for the formation of the stable phases. The spatial position of the (I)–(V) phase regions in the concentration space of the Ag–In–Te system relative to the position of silver was used to express the overall potential-forming reactions with the participation of the substances Ag, Te, In2Te5, Ag3In97Te147, AgIn5Te8, AgIn3Te5, and AgInTe2. The subsequent EMF measurements were carried out by applying the same GCs. The temperature dependences of the EMF of GCs with PE of the (I)–(V) phase regions were here used to determine, for the first time, the values of standard thermodynamic functions of the binary and ternary compounds. The determined values of the Gibbs energies of the formation of compounds are equal: (Formula presented.), (Formula presented.), (Formula presented.), (Formula presented.), and (Formula presented.) The correctness of the division of the equilibrium phase space of the Ag–In–Te system in the part AgInTe2–Te–In2Te3 involving the AgInTe2, AgIn3Te5, AgIn5Te8, and Ag3In97Te147 compounds was confirmed by the agreement of the calculated and literature-based thermodynamic data for In2Te5 compound. Compositions of pairs of the ternary compounds for their subsequent practical application were proposed.
KW - Ag-based compounds
KW - EMF method
KW - Gibbs free energy
KW - phase equilibria
KW - thermodynamic properties
KW - thermoelectric materials
UR - http://www.scopus.com/inward/record.url?scp=85141867866&partnerID=8YFLogxK
U2 - 10.3390/en15218180
DO - 10.3390/en15218180
M3 - Article
AN - SCOPUS:85141867866
SN - 1996-1073
VL - 15
JO - Energies
JF - Energies
IS - 21
M1 - 8180
ER -
