HiSuperBat - High-Capacity Electrodes for Aqueous Rechargeable Multivalent-Ion Batteries and Supercapacitors: Next Step Towards a Hybrid Model

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HiSuperBat - High-Capacity Electrodes for Aqueous Rechargeable Multivalent-Ion Batteries and Supercapacitors: Next Step Towards a Hybrid Model (en)
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Low-Cost Graphene-Based Composite Electrodes for Electrochemical Oxidation of Phenolic Dyes

Ječmenica Dučić, Marija; Krstić, Aleksandar D.; Zdolšek, Nikola; Aćimović, Danka; Savić, Branislava; Brdarić, Tanja; Vasić Anićijević, Dragana D.

(2023)

TY  - JOUR
AU  - Ječmenica Dučić, Marija
AU  - Krstić, Aleksandar D.
AU  - Zdolšek, Nikola
AU  - Aćimović, Danka
AU  - Savić, Branislava
AU  - Brdarić, Tanja
AU  - Vasić Anićijević, Dragana D.
PY  - 2023
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/10619
AB  - Electrochemical removal of organic pollutants represents an attractive methodology in water depollution. The key challenges for researchers comprise finding simple, affordable electrode materials with satisfactory efficiency in all ranges of pollutant concentration. Electrochemical oxidation of a mixture of phenol-based dyes: bromocresol green (BCG), cresol red (CR), and thymol blue (TB), in sulphate medium, at total concentration not exceeding 15 ppm, has been performed using simply prepared, low-cost composite electrodes, based on graphene nanoplatelets (GNP) and metallic oxides (TiO2 and SnO2) loaded on stainless steel substrate: GNP@SS, SnO2/GNP@SS, and TiO2/GNP@SS. Electrodes were characterised by XRD, FTIR, and electrochemical techniques. The degradation kinetics of initial dyes was tracked with UPLC and GC-MS chromatography for 6 h, at a current density of 10 mA/cm2. GC-MS analysis of the degradation products revealed oxidised aromatic compounds as the main products, while TOC analysis confirmed a total mineralisation extent in the range of 30–35%. The proposed degradation mechanism involves the attack of OH-radical, as the main oxidising agent, to the hydroxyl oxygens of dye phenolic rings. Obtained results provide useful information for the further development of affordable laboratory-scale and industrial systems for the complete removal of phenol-based compounds.
T2  - Crystals
T1  - Low-Cost Graphene-Based Composite Electrodes for Electrochemical Oxidation of Phenolic Dyes
VL  - 13
IS  - 1
SP  - 125
DO  - 10.3390/cryst13010125
ER  - 
@article{
author = "Ječmenica Dučić, Marija and Krstić, Aleksandar D. and Zdolšek, Nikola and Aćimović, Danka and Savić, Branislava and Brdarić, Tanja and Vasić Anićijević, Dragana D.",
year = "2023",
abstract = "Electrochemical removal of organic pollutants represents an attractive methodology in water depollution. The key challenges for researchers comprise finding simple, affordable electrode materials with satisfactory efficiency in all ranges of pollutant concentration. Electrochemical oxidation of a mixture of phenol-based dyes: bromocresol green (BCG), cresol red (CR), and thymol blue (TB), in sulphate medium, at total concentration not exceeding 15 ppm, has been performed using simply prepared, low-cost composite electrodes, based on graphene nanoplatelets (GNP) and metallic oxides (TiO2 and SnO2) loaded on stainless steel substrate: GNP@SS, SnO2/GNP@SS, and TiO2/GNP@SS. Electrodes were characterised by XRD, FTIR, and electrochemical techniques. The degradation kinetics of initial dyes was tracked with UPLC and GC-MS chromatography for 6 h, at a current density of 10 mA/cm2. GC-MS analysis of the degradation products revealed oxidised aromatic compounds as the main products, while TOC analysis confirmed a total mineralisation extent in the range of 30–35%. The proposed degradation mechanism involves the attack of OH-radical, as the main oxidising agent, to the hydroxyl oxygens of dye phenolic rings. Obtained results provide useful information for the further development of affordable laboratory-scale and industrial systems for the complete removal of phenol-based compounds.",
journal = "Crystals",
title = "Low-Cost Graphene-Based Composite Electrodes for Electrochemical Oxidation of Phenolic Dyes",
volume = "13",
number = "1",
pages = "125",
doi = "10.3390/cryst13010125"
}
Ječmenica Dučić, M., Krstić, A. D., Zdolšek, N., Aćimović, D., Savić, B., Brdarić, T.,& Vasić Anićijević, D. D.. (2023). Low-Cost Graphene-Based Composite Electrodes for Electrochemical Oxidation of Phenolic Dyes. in Crystals, 13(1), 125.
https://doi.org/10.3390/cryst13010125
Ječmenica Dučić M, Krstić AD, Zdolšek N, Aćimović D, Savić B, Brdarić T, Vasić Anićijević DD. Low-Cost Graphene-Based Composite Electrodes for Electrochemical Oxidation of Phenolic Dyes. in Crystals. 2023;13(1):125.
doi:10.3390/cryst13010125 .
Ječmenica Dučić, Marija, Krstić, Aleksandar D., Zdolšek, Nikola, Aćimović, Danka, Savić, Branislava, Brdarić, Tanja, Vasić Anićijević, Dragana D., "Low-Cost Graphene-Based Composite Electrodes for Electrochemical Oxidation of Phenolic Dyes" in Crystals, 13, no. 1 (2023):125,
https://doi.org/10.3390/cryst13010125 . .
1
1

Thermal decomposition kinetics of deep eutectic solvent (DES) based on choline chloride and magnesium chloride hexahydrate: New details on the reaction mechanism and enthalpy–entropy compensation (EEC)

Janković, Bojan Ž.; Manić, Nebojša; Perović, Ivana M.; Vujković, Milica; Zdolšek, Nikola

(2023)

TY  - JOUR
AU  - Janković, Bojan Ž.
AU  - Manić, Nebojša
AU  - Perović, Ivana M.
AU  - Vujković, Milica
AU  - Zdolšek, Nikola
PY  - 2023
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/10739
AB  - In recent years, deep eutectic solvents (DESs) have attracted considerable attention, and they have been applied in many fields, such as dissolution and separation, electrochemistry, materials preparation, reaction, and catalysis. In this paper, a detailed thermal decomposition mechanism of DES-type II (consisting choline chloride (ChCl) and magnesium chloride hexahydrate (MgCl2·6H2O) in a molar ratio 2:1 (MgCl2·6H2O-[Ch]Cl)) was explained, using thermal analysis techniques. Physicochemical clarification of overall thermal decomposition mechanism and the influence of enthalpy–entropy compensation (EEC) on reactions mechanism emerging are presented for the first time, in favor of this DES type. In the kinetic analysis of the decomposition process, two approaches were used: model-free (inverse) and model-based (direct) methods. It was found that thermodynamic principles in the form of EEC are the source of kinetic compensation effect (KCE) during MgCl2·6H2O-[Ch]Cl thermal decomposition, as a consequence of the effects of molecular interactions. Key phenomenon in the complex multiple step process represents a parallel dehydration steps of MgCl2·6H2O in DES, leading to formation of intermediates, such as [MgCl1(H2O)5]1+ and [MgCl2(H2O)4]. It was established that formation of final products (Mg(OH)2 and MgOHCl) requires a higher expenditure of energy to overcome a high potential barrier, where reaction system compensates this energy via hydrogen bonding disruption. This was confirmed by the identification of a specific ‘oscillator’, flagged as Hsingle bondOsingle bondH···Cl hydrogen bond donating system of the energy (“heat bath”). All kinetic parameters and mechanisms of individual reaction steps were confirmed by numerical optimization of the process and modulated dynamic predictions.
T2  - Journal of Molecular Liquids
T1  - Thermal decomposition kinetics of deep eutectic solvent (DES) based on choline chloride and magnesium chloride hexahydrate: New details on the reaction mechanism and enthalpy–entropy compensation (EEC)
VL  - 374
SP  - 121274
DO  - 10.1016/j.molliq.2023.121274
ER  - 
@article{
author = "Janković, Bojan Ž. and Manić, Nebojša and Perović, Ivana M. and Vujković, Milica and Zdolšek, Nikola",
year = "2023",
abstract = "In recent years, deep eutectic solvents (DESs) have attracted considerable attention, and they have been applied in many fields, such as dissolution and separation, electrochemistry, materials preparation, reaction, and catalysis. In this paper, a detailed thermal decomposition mechanism of DES-type II (consisting choline chloride (ChCl) and magnesium chloride hexahydrate (MgCl2·6H2O) in a molar ratio 2:1 (MgCl2·6H2O-[Ch]Cl)) was explained, using thermal analysis techniques. Physicochemical clarification of overall thermal decomposition mechanism and the influence of enthalpy–entropy compensation (EEC) on reactions mechanism emerging are presented for the first time, in favor of this DES type. In the kinetic analysis of the decomposition process, two approaches were used: model-free (inverse) and model-based (direct) methods. It was found that thermodynamic principles in the form of EEC are the source of kinetic compensation effect (KCE) during MgCl2·6H2O-[Ch]Cl thermal decomposition, as a consequence of the effects of molecular interactions. Key phenomenon in the complex multiple step process represents a parallel dehydration steps of MgCl2·6H2O in DES, leading to formation of intermediates, such as [MgCl1(H2O)5]1+ and [MgCl2(H2O)4]. It was established that formation of final products (Mg(OH)2 and MgOHCl) requires a higher expenditure of energy to overcome a high potential barrier, where reaction system compensates this energy via hydrogen bonding disruption. This was confirmed by the identification of a specific ‘oscillator’, flagged as Hsingle bondOsingle bondH···Cl hydrogen bond donating system of the energy (“heat bath”). All kinetic parameters and mechanisms of individual reaction steps were confirmed by numerical optimization of the process and modulated dynamic predictions.",
journal = "Journal of Molecular Liquids",
title = "Thermal decomposition kinetics of deep eutectic solvent (DES) based on choline chloride and magnesium chloride hexahydrate: New details on the reaction mechanism and enthalpy–entropy compensation (EEC)",
volume = "374",
pages = "121274",
doi = "10.1016/j.molliq.2023.121274"
}
Janković, B. Ž., Manić, N., Perović, I. M., Vujković, M.,& Zdolšek, N.. (2023). Thermal decomposition kinetics of deep eutectic solvent (DES) based on choline chloride and magnesium chloride hexahydrate: New details on the reaction mechanism and enthalpy–entropy compensation (EEC). in Journal of Molecular Liquids, 374, 121274.
https://doi.org/10.1016/j.molliq.2023.121274
Janković BŽ, Manić N, Perović IM, Vujković M, Zdolšek N. Thermal decomposition kinetics of deep eutectic solvent (DES) based on choline chloride and magnesium chloride hexahydrate: New details on the reaction mechanism and enthalpy–entropy compensation (EEC). in Journal of Molecular Liquids. 2023;374:121274.
doi:10.1016/j.molliq.2023.121274 .
Janković, Bojan Ž., Manić, Nebojša, Perović, Ivana M., Vujković, Milica, Zdolšek, Nikola, "Thermal decomposition kinetics of deep eutectic solvent (DES) based on choline chloride and magnesium chloride hexahydrate: New details on the reaction mechanism and enthalpy–entropy compensation (EEC)" in Journal of Molecular Liquids, 374 (2023):121274,
https://doi.org/10.1016/j.molliq.2023.121274 . .
5
5

Deep Eutectic Solvent for Facile Synthesis of Mn3O4@N-Doped Carbon for Aqueous Multivalent-Based Supercapacitors: New Concept for Increasing Capacitance and Operating Voltage

Zdolšek, Nikola; Perović, Ivana; Brković, Snežana M.; Tasić, Gvozden S.; Milović, Miloš; Vujković, Milica

(2022)

TY  - JOUR
AU  - Zdolšek, Nikola
AU  - Perović, Ivana
AU  - Brković, Snežana M.
AU  - Tasić, Gvozden S.
AU  - Milović, Miloš
AU  - Vujković, Milica
PY  - 2022
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/11004
AB  - The capacitance and operating voltage of supercapacitors as well as their energy density have been increased by development of different materials and electrolytes. In this paper, two strategies, for the first time, were used to improve energy density: Mn3O4- and N-dual doped carbon electrode and aqueous mixture of multivalent ions as electrolyte. Mn3O4- and N-dual doped carbon was prepared by a novel and cost-effective procedure using deep eutectic solvent. XRD, XPS, and FTIR confirmed presence of Mn3O4 and nitrogen, while SEM and EDS elemental mapping showed micrometer-sized nanosheets with uniform distribution of C, O, N, and Mn atoms. Charge storage behavior of carbon was tested in aqueous multivalent-based electrolytes and their mixture (Ca2+-Al3+). Regarding both specific capacitance and workable voltage, the Ca2+-Al3+ mixed electrolyte was found as the best optimal solution. The calcium addition to the Al-electrolyte allows the higher operating voltage than in the case of individual Al(NO3)3 electrolyte while the addition of Al3+ ion in the Ca(NO3)2 electrolyte improves the multivalent-ion charge storage ability of carbon. As a result, the specific energy density of two-electrode Mn3O4@N-doped carbon//Al(NO3)2+Ca(NO3)2//Mn3O4@N-doped carbon supercapacitor (34 Wh kg−1 at 0.1 A g−1) overpasses the reported values obtained for Mn-based carbon supercapacitors using conventional aqueous electrolytes.
T2  - Materials
T1  - Deep Eutectic Solvent for Facile Synthesis of Mn3O4@N-Doped Carbon for Aqueous Multivalent-Based Supercapacitors: New Concept for Increasing Capacitance and Operating Voltage
VL  - 15
IS  - 23
SP  - 8540
DO  - 10.3390/ma15238540
ER  - 
@article{
author = "Zdolšek, Nikola and Perović, Ivana and Brković, Snežana M. and Tasić, Gvozden S. and Milović, Miloš and Vujković, Milica",
year = "2022",
abstract = "The capacitance and operating voltage of supercapacitors as well as their energy density have been increased by development of different materials and electrolytes. In this paper, two strategies, for the first time, were used to improve energy density: Mn3O4- and N-dual doped carbon electrode and aqueous mixture of multivalent ions as electrolyte. Mn3O4- and N-dual doped carbon was prepared by a novel and cost-effective procedure using deep eutectic solvent. XRD, XPS, and FTIR confirmed presence of Mn3O4 and nitrogen, while SEM and EDS elemental mapping showed micrometer-sized nanosheets with uniform distribution of C, O, N, and Mn atoms. Charge storage behavior of carbon was tested in aqueous multivalent-based electrolytes and their mixture (Ca2+-Al3+). Regarding both specific capacitance and workable voltage, the Ca2+-Al3+ mixed electrolyte was found as the best optimal solution. The calcium addition to the Al-electrolyte allows the higher operating voltage than in the case of individual Al(NO3)3 electrolyte while the addition of Al3+ ion in the Ca(NO3)2 electrolyte improves the multivalent-ion charge storage ability of carbon. As a result, the specific energy density of two-electrode Mn3O4@N-doped carbon//Al(NO3)2+Ca(NO3)2//Mn3O4@N-doped carbon supercapacitor (34 Wh kg−1 at 0.1 A g−1) overpasses the reported values obtained for Mn-based carbon supercapacitors using conventional aqueous electrolytes.",
journal = "Materials",
title = "Deep Eutectic Solvent for Facile Synthesis of Mn3O4@N-Doped Carbon for Aqueous Multivalent-Based Supercapacitors: New Concept for Increasing Capacitance and Operating Voltage",
volume = "15",
number = "23",
pages = "8540",
doi = "10.3390/ma15238540"
}
Zdolšek, N., Perović, I., Brković, S. M., Tasić, G. S., Milović, M.,& Vujković, M.. (2022). Deep Eutectic Solvent for Facile Synthesis of Mn3O4@N-Doped Carbon for Aqueous Multivalent-Based Supercapacitors: New Concept for Increasing Capacitance and Operating Voltage. in Materials, 15(23), 8540.
https://doi.org/10.3390/ma15238540
Zdolšek N, Perović I, Brković SM, Tasić GS, Milović M, Vujković M. Deep Eutectic Solvent for Facile Synthesis of Mn3O4@N-Doped Carbon for Aqueous Multivalent-Based Supercapacitors: New Concept for Increasing Capacitance and Operating Voltage. in Materials. 2022;15(23):8540.
doi:10.3390/ma15238540 .
Zdolšek, Nikola, Perović, Ivana, Brković, Snežana M., Tasić, Gvozden S., Milović, Miloš, Vujković, Milica, "Deep Eutectic Solvent for Facile Synthesis of Mn3O4@N-Doped Carbon for Aqueous Multivalent-Based Supercapacitors: New Concept for Increasing Capacitance and Operating Voltage" in Materials, 15, no. 23 (2022):8540,
https://doi.org/10.3390/ma15238540 . .
3
3

Deep Eutectic Solvent (DES) for In Situ Templating Carbon Material: Carbon Characterization and Application in Supercapacitors Containing Multivalent Ions

Zdolšek, Nikola; Janković, Bojan Ž.; Milović, Miloš; Brković, Snežana M.; Krstić, Jugoslav B.; Perović, Ivana M.; Vujković, Milica

(2022)

TY  - JOUR
AU  - Zdolšek, Nikola
AU  - Janković, Bojan Ž.
AU  - Milović, Miloš
AU  - Brković, Snežana M.
AU  - Krstić, Jugoslav B.
AU  - Perović, Ivana M.
AU  - Vujković, Milica
PY  - 2022
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/10571
AB  - The development of carbon materials with desirable textures and new aqueous electrolytes is the key strategy to improve the performance of supercapacitors. Herein, a deep eutectic solvent (DES) was used for in situ templating of a carbon material. A carbon material was characterized (XRD, N2-physisorption, FTIR, SEM and EDS) and used as an electrode material for the first time in multivalent-based supercapacitors. In situ templating of carbon was performed using a novel DES, which serves as a precursor for carbon and for in situ generation of MgO. The generation of MgO and its roles in templating of carbon were discussed. Templating of carbon with MgO lead to an increase in surface area and a microporous texture. The obtained carbon was tested in multivalent-ion (Al3+ and Mg2+) electrolytes and compared with H2SO4. The charge-storage mechanism was investigated and elaborated. The highest specific capacitance was obtained for the Al(NO3)3 electrolyte, while the operating voltage follows the order: Mg(NO3)2 > Al(NO3)3 > H2SO4. Electrical double-layer capacitance (versus pseudocapacitance) was dominant in all investigated electrolytes. The larger operating voltage in multivalent electrolytes is a consequence of the lower fraction of free water, which suppresses hydrogen evolution (when compared with H2SO4). The GCD was experimentally performed on the Al(NO3)3 electrolyte, which showed good cyclic stability, with an energy density of 22.3 Wh kg−1 at 65 W kg−1.
T2  - Batteries
T1  - Deep Eutectic Solvent (DES) for In Situ Templating Carbon Material: Carbon Characterization and Application in Supercapacitors Containing Multivalent Ions
VL  - 8
IS  - 12
SP  - 284
DO  - 10.3390/batteries8120284
ER  - 
@article{
author = "Zdolšek, Nikola and Janković, Bojan Ž. and Milović, Miloš and Brković, Snežana M. and Krstić, Jugoslav B. and Perović, Ivana M. and Vujković, Milica",
year = "2022",
abstract = "The development of carbon materials with desirable textures and new aqueous electrolytes is the key strategy to improve the performance of supercapacitors. Herein, a deep eutectic solvent (DES) was used for in situ templating of a carbon material. A carbon material was characterized (XRD, N2-physisorption, FTIR, SEM and EDS) and used as an electrode material for the first time in multivalent-based supercapacitors. In situ templating of carbon was performed using a novel DES, which serves as a precursor for carbon and for in situ generation of MgO. The generation of MgO and its roles in templating of carbon were discussed. Templating of carbon with MgO lead to an increase in surface area and a microporous texture. The obtained carbon was tested in multivalent-ion (Al3+ and Mg2+) electrolytes and compared with H2SO4. The charge-storage mechanism was investigated and elaborated. The highest specific capacitance was obtained for the Al(NO3)3 electrolyte, while the operating voltage follows the order: Mg(NO3)2 > Al(NO3)3 > H2SO4. Electrical double-layer capacitance (versus pseudocapacitance) was dominant in all investigated electrolytes. The larger operating voltage in multivalent electrolytes is a consequence of the lower fraction of free water, which suppresses hydrogen evolution (when compared with H2SO4). The GCD was experimentally performed on the Al(NO3)3 electrolyte, which showed good cyclic stability, with an energy density of 22.3 Wh kg−1 at 65 W kg−1.",
journal = "Batteries",
title = "Deep Eutectic Solvent (DES) for In Situ Templating Carbon Material: Carbon Characterization and Application in Supercapacitors Containing Multivalent Ions",
volume = "8",
number = "12",
pages = "284",
doi = "10.3390/batteries8120284"
}
Zdolšek, N., Janković, B. Ž., Milović, M., Brković, S. M., Krstić, J. B., Perović, I. M.,& Vujković, M.. (2022). Deep Eutectic Solvent (DES) for In Situ Templating Carbon Material: Carbon Characterization and Application in Supercapacitors Containing Multivalent Ions. in Batteries, 8(12), 284.
https://doi.org/10.3390/batteries8120284
Zdolšek N, Janković BŽ, Milović M, Brković SM, Krstić JB, Perović IM, Vujković M. Deep Eutectic Solvent (DES) for In Situ Templating Carbon Material: Carbon Characterization and Application in Supercapacitors Containing Multivalent Ions. in Batteries. 2022;8(12):284.
doi:10.3390/batteries8120284 .
Zdolšek, Nikola, Janković, Bojan Ž., Milović, Miloš, Brković, Snežana M., Krstić, Jugoslav B., Perović, Ivana M., Vujković, Milica, "Deep Eutectic Solvent (DES) for In Situ Templating Carbon Material: Carbon Characterization and Application in Supercapacitors Containing Multivalent Ions" in Batteries, 8, no. 12 (2022):284,
https://doi.org/10.3390/batteries8120284 . .

Crystal Structure and Electrical Properties of Ruthenium-Substituted Calcium Copper Titanate

Veselinović, Ljiljana; Mitrić, Miodrag; Mančić, Lidija; Jardim, Paula M.; Škapin, Srečo Davor; Cvjetićanin, Nikola; Milović, Miloš D.; Marković, Smilja

(2022)

TY  - JOUR
AU  - Veselinović, Ljiljana
AU  - Mitrić, Miodrag
AU  - Mančić, Lidija
AU  - Jardim, Paula M.
AU  - Škapin, Srečo Davor
AU  - Cvjetićanin, Nikola
AU  - Milović, Miloš D.
AU  - Marković, Smilja
PY  - 2022
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/12382
AB  - This paper reports a detailed study of crystal structure and dielectric properties of ruthenium-substituted calcium-copper titanates (CaCu3Ti4−xRuxO12, CCTRO). A series of three samples with different stoichiometry was prepared: CaCu3Ti4−xRuxO12, x = 0, 1 and 4, abbreviated as CCTO, CCT3RO and CCRO, respectively. A detailed structural analysis of CCTRO samples was done by the Rietveld refinement of XRPD data. The results show that, regardless of whether Ti4+ or Ru4+ ions are placed in B crystallographic position in AA’3B4O12 (CaCu3Ti4−xRuxO12) unit cell, the crystal structure remains cubic with Im3¯ symmetry. Slight increases in the unit cell parameters, cell volume and interatomic distances indicate that Ru4+ ions with larger ionic radii (0.62 Å) than Ti4+ (0.605 Å) are incorporated in the CaCu3Ti4−xRuxO12 crystal lattice. The structural investigations were confirmed using TEM, HRTEM and ADF/STEM analyses, including EDXS elemental mapping. The effect of Ru atoms share in CaCu3Ti4−xRuxO12 samples on their electrical properties was determined by impedance and dielectric measurements. Results of dielectric measurements indicate that one atom of ruthenium per CaCu3Ti4−xRuxO12 unit cell transforms dielectric CCTO into conductive CCT3RO while preserving cubic crystal structure. Our findings about CCTO and CCT3RO ceramics promote them as ideal tandem to overcome the problem of stress on dielectric-electrode interfaces in capacitors.
T2  - Materials
T1  - Crystal Structure and Electrical Properties of Ruthenium-Substituted Calcium Copper Titanate
VL  - 15
IS  - 23
SP  - 8500
SP  - 8500
DO  - 10.3390/ma15238500
ER  - 
@article{
author = "Veselinović, Ljiljana and Mitrić, Miodrag and Mančić, Lidija and Jardim, Paula M. and Škapin, Srečo Davor and Cvjetićanin, Nikola and Milović, Miloš D. and Marković, Smilja",
year = "2022",
abstract = "This paper reports a detailed study of crystal structure and dielectric properties of ruthenium-substituted calcium-copper titanates (CaCu3Ti4−xRuxO12, CCTRO). A series of three samples with different stoichiometry was prepared: CaCu3Ti4−xRuxO12, x = 0, 1 and 4, abbreviated as CCTO, CCT3RO and CCRO, respectively. A detailed structural analysis of CCTRO samples was done by the Rietveld refinement of XRPD data. The results show that, regardless of whether Ti4+ or Ru4+ ions are placed in B crystallographic position in AA’3B4O12 (CaCu3Ti4−xRuxO12) unit cell, the crystal structure remains cubic with Im3¯ symmetry. Slight increases in the unit cell parameters, cell volume and interatomic distances indicate that Ru4+ ions with larger ionic radii (0.62 Å) than Ti4+ (0.605 Å) are incorporated in the CaCu3Ti4−xRuxO12 crystal lattice. The structural investigations were confirmed using TEM, HRTEM and ADF/STEM analyses, including EDXS elemental mapping. The effect of Ru atoms share in CaCu3Ti4−xRuxO12 samples on their electrical properties was determined by impedance and dielectric measurements. Results of dielectric measurements indicate that one atom of ruthenium per CaCu3Ti4−xRuxO12 unit cell transforms dielectric CCTO into conductive CCT3RO while preserving cubic crystal structure. Our findings about CCTO and CCT3RO ceramics promote them as ideal tandem to overcome the problem of stress on dielectric-electrode interfaces in capacitors.",
journal = "Materials",
title = "Crystal Structure and Electrical Properties of Ruthenium-Substituted Calcium Copper Titanate",
volume = "15",
number = "23",
pages = "8500-8500",
doi = "10.3390/ma15238500"
}
Veselinović, L., Mitrić, M., Mančić, L., Jardim, P. M., Škapin, S. D., Cvjetićanin, N., Milović, M. D.,& Marković, S.. (2022). Crystal Structure and Electrical Properties of Ruthenium-Substituted Calcium Copper Titanate. in Materials, 15(23), 8500.
https://doi.org/10.3390/ma15238500
Veselinović L, Mitrić M, Mančić L, Jardim PM, Škapin SD, Cvjetićanin N, Milović MD, Marković S. Crystal Structure and Electrical Properties of Ruthenium-Substituted Calcium Copper Titanate. in Materials. 2022;15(23):8500.
doi:10.3390/ma15238500 .
Veselinović, Ljiljana, Mitrić, Miodrag, Mančić, Lidija, Jardim, Paula M., Škapin, Srečo Davor, Cvjetićanin, Nikola, Milović, Miloš D., Marković, Smilja, "Crystal Structure and Electrical Properties of Ruthenium-Substituted Calcium Copper Titanate" in Materials, 15, no. 23 (2022):8500,
https://doi.org/10.3390/ma15238500 . .

Boosting electrocatalysis of oxygen reduction and evolution reactions with cost-effective cobalt and nitrogen-doped carbons prepared by simple carbonization of ionic liquids

Zdolšek, Nikola; Vujković, Milica; Metin, Önder; Brković, Snežana; Jocić, Ana; Dimitrijević, Aleksandra; Trtić-Petrović, Tatjana M.; Šljukić, Biljana

(2022)

TY  - JOUR
AU  - Zdolšek, Nikola
AU  - Vujković, Milica
AU  - Metin, Önder
AU  - Brković, Snežana
AU  - Jocić, Ana
AU  - Dimitrijević, Aleksandra
AU  - Trtić-Petrović, Tatjana M.
AU  - Šljukić, Biljana
PY  - 2022
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/10229
AB  - Development of cost-effective, bi-functional carbon electrocatalysts via direct carbonization of ionic liquids (bis(cholinium) tetrachlorocobaltate(II) ([Ch]2[CoCl4]) and bis(1-butyl-3-methylimidazolium) tetrachlorocobaltate(II) ([Bmim]2[CoCl4])) is reported herein for the first time. Carbon electrocatalysts, dual-doped with cobalt and nitrogen, were tested for oxygen reduction (ORR) and oxygen evolution (OER) reactions. Both materials show high bi-functional catalytic activity and excellent stability due to synergistic effects arising from the presence of nitrogen and cobalt. Electrocatalyst prepared by carbonization of [Ch]2[CoCl4] show exceptional activity and selectivity toward ORR. Conversely, electrocatalyst prepared from [Bmim]2[CoCl4] showed a slightly better OER performance indicating that different catalytic sites are responsible for O2 reduction and H2O oxidation. Parent CoO particles with graphitic nitrogen boost activity for ORR, while elemental Co supported by nitrogen atoms is responsible for OER activity. Finally, energy consumption during electrolytic oxygen production was calculated revealing energy saving when using two materials as anode electrocatalysts.
T2  - International Journal of Hydrogen Energy
T1  - Boosting electrocatalysis of oxygen reduction and evolution reactions with cost-effective cobalt and nitrogen-doped carbons prepared by simple carbonization of ionic liquids
VL  - 47
IS  - 33
SP  - 14847
EP  - 14858
DO  - 10.1016/j.ijhydene.2022.02.225
ER  - 
@article{
author = "Zdolšek, Nikola and Vujković, Milica and Metin, Önder and Brković, Snežana and Jocić, Ana and Dimitrijević, Aleksandra and Trtić-Petrović, Tatjana M. and Šljukić, Biljana",
year = "2022",
abstract = "Development of cost-effective, bi-functional carbon electrocatalysts via direct carbonization of ionic liquids (bis(cholinium) tetrachlorocobaltate(II) ([Ch]2[CoCl4]) and bis(1-butyl-3-methylimidazolium) tetrachlorocobaltate(II) ([Bmim]2[CoCl4])) is reported herein for the first time. Carbon electrocatalysts, dual-doped with cobalt and nitrogen, were tested for oxygen reduction (ORR) and oxygen evolution (OER) reactions. Both materials show high bi-functional catalytic activity and excellent stability due to synergistic effects arising from the presence of nitrogen and cobalt. Electrocatalyst prepared by carbonization of [Ch]2[CoCl4] show exceptional activity and selectivity toward ORR. Conversely, electrocatalyst prepared from [Bmim]2[CoCl4] showed a slightly better OER performance indicating that different catalytic sites are responsible for O2 reduction and H2O oxidation. Parent CoO particles with graphitic nitrogen boost activity for ORR, while elemental Co supported by nitrogen atoms is responsible for OER activity. Finally, energy consumption during electrolytic oxygen production was calculated revealing energy saving when using two materials as anode electrocatalysts.",
journal = "International Journal of Hydrogen Energy",
title = "Boosting electrocatalysis of oxygen reduction and evolution reactions with cost-effective cobalt and nitrogen-doped carbons prepared by simple carbonization of ionic liquids",
volume = "47",
number = "33",
pages = "14847-14858",
doi = "10.1016/j.ijhydene.2022.02.225"
}
Zdolšek, N., Vujković, M., Metin, Ö., Brković, S., Jocić, A., Dimitrijević, A., Trtić-Petrović, T. M.,& Šljukić, B.. (2022). Boosting electrocatalysis of oxygen reduction and evolution reactions with cost-effective cobalt and nitrogen-doped carbons prepared by simple carbonization of ionic liquids. in International Journal of Hydrogen Energy, 47(33), 14847-14858.
https://doi.org/10.1016/j.ijhydene.2022.02.225
Zdolšek N, Vujković M, Metin Ö, Brković S, Jocić A, Dimitrijević A, Trtić-Petrović TM, Šljukić B. Boosting electrocatalysis of oxygen reduction and evolution reactions with cost-effective cobalt and nitrogen-doped carbons prepared by simple carbonization of ionic liquids. in International Journal of Hydrogen Energy. 2022;47(33):14847-14858.
doi:10.1016/j.ijhydene.2022.02.225 .
Zdolšek, Nikola, Vujković, Milica, Metin, Önder, Brković, Snežana, Jocić, Ana, Dimitrijević, Aleksandra, Trtić-Petrović, Tatjana M., Šljukić, Biljana, "Boosting electrocatalysis of oxygen reduction and evolution reactions with cost-effective cobalt and nitrogen-doped carbons prepared by simple carbonization of ionic liquids" in International Journal of Hydrogen Energy, 47, no. 33 (2022):14847-14858,
https://doi.org/10.1016/j.ijhydene.2022.02.225 . .
6
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The Influence of a Binder in a Composite Electrode: The Case Study of Vanadyl Phosphate in Aqueous Electrolyte

Jugović, Dragana; Milović, Miloš; Barudžija, Tanja; Kuzmanović, Maja; Vujković, Milica; Mitrić, Miodrag

(2022)

TY  - JOUR
AU  - Jugović, Dragana
AU  - Milović, Miloš
AU  - Barudžija, Tanja
AU  - Kuzmanović, Maja
AU  - Vujković, Milica
AU  - Mitrić, Miodrag
PY  - 2022
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/10577
AB  - Layered VOPO4·2H2O is synthesized by the sonochemical method. An X-ray powder diffraction is used to examine the crystal structure, while scanning electron microscopy is used to reveal the morphology of the powder. The crystal structure refinement is performed in the P4/nmmZ space group. The electrochemical intercalation of several cations (Na+, Mg2+, Ca2+, and Al3+) in saturated nitrate aqueous solutions is investigated. The most notable reversible activity is found for the cycling in aluminium nitrate aqueous solution in the voltage range from −0.1 to 0.8 V vs. SCE. During the preparation of the electrode, it is observed that the structure is prone to changes that have not been recorded in the literature so far. Namely, the use of conventional binder PVDF in NMP solution deteriorates the structure and lowers the powder’s crystallinity, while the use of Nafion solution causes the rearrangement of the atoms in a new crystal form that can be described in the monoclinic P21/c space group. Consequently, these structural changes affect electrochemical performances. The observed differences in electrochemical performances are a result of structural rearrangements.
T2  - Materials
T1  - The Influence of a Binder in a Composite Electrode: The Case Study of Vanadyl Phosphate in Aqueous Electrolyte
VL  - 15
IS  - 24
SP  - 9041
DO  - 10.3390/ma15249041
ER  - 
@article{
author = "Jugović, Dragana and Milović, Miloš and Barudžija, Tanja and Kuzmanović, Maja and Vujković, Milica and Mitrić, Miodrag",
year = "2022",
abstract = "Layered VOPO4·2H2O is synthesized by the sonochemical method. An X-ray powder diffraction is used to examine the crystal structure, while scanning electron microscopy is used to reveal the morphology of the powder. The crystal structure refinement is performed in the P4/nmmZ space group. The electrochemical intercalation of several cations (Na+, Mg2+, Ca2+, and Al3+) in saturated nitrate aqueous solutions is investigated. The most notable reversible activity is found for the cycling in aluminium nitrate aqueous solution in the voltage range from −0.1 to 0.8 V vs. SCE. During the preparation of the electrode, it is observed that the structure is prone to changes that have not been recorded in the literature so far. Namely, the use of conventional binder PVDF in NMP solution deteriorates the structure and lowers the powder’s crystallinity, while the use of Nafion solution causes the rearrangement of the atoms in a new crystal form that can be described in the monoclinic P21/c space group. Consequently, these structural changes affect electrochemical performances. The observed differences in electrochemical performances are a result of structural rearrangements.",
journal = "Materials",
title = "The Influence of a Binder in a Composite Electrode: The Case Study of Vanadyl Phosphate in Aqueous Electrolyte",
volume = "15",
number = "24",
pages = "9041",
doi = "10.3390/ma15249041"
}
Jugović, D., Milović, M., Barudžija, T., Kuzmanović, M., Vujković, M.,& Mitrić, M.. (2022). The Influence of a Binder in a Composite Electrode: The Case Study of Vanadyl Phosphate in Aqueous Electrolyte. in Materials, 15(24), 9041.
https://doi.org/10.3390/ma15249041
Jugović D, Milović M, Barudžija T, Kuzmanović M, Vujković M, Mitrić M. The Influence of a Binder in a Composite Electrode: The Case Study of Vanadyl Phosphate in Aqueous Electrolyte. in Materials. 2022;15(24):9041.
doi:10.3390/ma15249041 .
Jugović, Dragana, Milović, Miloš, Barudžija, Tanja, Kuzmanović, Maja, Vujković, Milica, Mitrić, Miodrag, "The Influence of a Binder in a Composite Electrode: The Case Study of Vanadyl Phosphate in Aqueous Electrolyte" in Materials, 15, no. 24 (2022):9041,
https://doi.org/10.3390/ma15249041 . .
1

Polyaniline as a charge storage material in an aqueous aluminum-based electrolyte: Can aluminum ions play the role of protons?

Vujković, Milica ; Etinski, Mihajlo; Vasić, Borislav; Kuzmanović, Bojana; Bajuk-Bogdanović, Danica V.; Dominko, Robert; Mentus, Slavko V.

(2021)

TY  - JOUR
AU  - Vujković, Milica 
AU  - Etinski, Mihajlo
AU  - Vasić, Borislav
AU  - Kuzmanović, Bojana
AU  - Bajuk-Bogdanović, Danica V.
AU  - Dominko, Robert
AU  - Mentus, Slavko V.
PY  - 2021
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/9645
AB  - The high redox activity of polyaniline emeraldine salt (PANI-ES) was revealed in the aqueous solution of Al-salt, which makes this polymer attractive as an electrode material for aqueous aluminum electrochemical storage devices. Its redox behavior in Al(NO3)3, Al(NO3)3+HCl, AlCl3 and HCl was investigated by Cyclic Voltammetry and Chronopotentiometry. While the proton exchange determines PANI's redox behavior in strong acidic solutions, anion doping/dedoping is a more dominant process in less acidic Al-salt solutions. The formation/dissolution of solid-state nitrate complexes is proposed to happen during PANI's redox switching in Al(NO3)3, which causes disappearance and reappearance of grain boundaries, as revealed by AFM. Combined experimental and DFT approaches identify Al-salt as a secondary dopant of protonated PANI-ES (by Lewis acid-base complexation), which causes polaron→bipolaron conversion. The change in the redox mechanism of PANI-ES, caused by the substitution of HCl with Al(NO3)3, did not attenuate its charge storage ability. Moreover, PANI-ES delivers a higher capacitance in Al(NO3)3, amounting to 269 F g−1 at 10 A g−1. Furthermore, the use of Al(NO3)3 results in attenuated electrochemical PANI overoxidation, when compared to HCl, thus providing better capacitance retention upon potentiodynamic cycling. The results open novel perspective of using PANI-based materials for more suitable energy storage devices.
T2  - Journal of Power Sources
T1  - Polyaniline as a charge storage material in an aqueous aluminum-based electrolyte: Can aluminum ions play the role of protons?
VL  - 482
SP  - 228937
DO  - 10.1016/j.jpowsour.2020.228937
ER  - 
@article{
author = "Vujković, Milica  and Etinski, Mihajlo and Vasić, Borislav and Kuzmanović, Bojana and Bajuk-Bogdanović, Danica V. and Dominko, Robert and Mentus, Slavko V.",
year = "2021",
abstract = "The high redox activity of polyaniline emeraldine salt (PANI-ES) was revealed in the aqueous solution of Al-salt, which makes this polymer attractive as an electrode material for aqueous aluminum electrochemical storage devices. Its redox behavior in Al(NO3)3, Al(NO3)3+HCl, AlCl3 and HCl was investigated by Cyclic Voltammetry and Chronopotentiometry. While the proton exchange determines PANI's redox behavior in strong acidic solutions, anion doping/dedoping is a more dominant process in less acidic Al-salt solutions. The formation/dissolution of solid-state nitrate complexes is proposed to happen during PANI's redox switching in Al(NO3)3, which causes disappearance and reappearance of grain boundaries, as revealed by AFM. Combined experimental and DFT approaches identify Al-salt as a secondary dopant of protonated PANI-ES (by Lewis acid-base complexation), which causes polaron→bipolaron conversion. The change in the redox mechanism of PANI-ES, caused by the substitution of HCl with Al(NO3)3, did not attenuate its charge storage ability. Moreover, PANI-ES delivers a higher capacitance in Al(NO3)3, amounting to 269 F g−1 at 10 A g−1. Furthermore, the use of Al(NO3)3 results in attenuated electrochemical PANI overoxidation, when compared to HCl, thus providing better capacitance retention upon potentiodynamic cycling. The results open novel perspective of using PANI-based materials for more suitable energy storage devices.",
journal = "Journal of Power Sources",
title = "Polyaniline as a charge storage material in an aqueous aluminum-based electrolyte: Can aluminum ions play the role of protons?",
volume = "482",
pages = "228937",
doi = "10.1016/j.jpowsour.2020.228937"
}
Vujković, M., Etinski, M., Vasić, B., Kuzmanović, B., Bajuk-Bogdanović, D. V., Dominko, R.,& Mentus, S. V.. (2021). Polyaniline as a charge storage material in an aqueous aluminum-based electrolyte: Can aluminum ions play the role of protons?. in Journal of Power Sources, 482, 228937.
https://doi.org/10.1016/j.jpowsour.2020.228937
Vujković M, Etinski M, Vasić B, Kuzmanović B, Bajuk-Bogdanović DV, Dominko R, Mentus SV. Polyaniline as a charge storage material in an aqueous aluminum-based electrolyte: Can aluminum ions play the role of protons?. in Journal of Power Sources. 2021;482:228937.
doi:10.1016/j.jpowsour.2020.228937 .
Vujković, Milica , Etinski, Mihajlo, Vasić, Borislav, Kuzmanović, Bojana, Bajuk-Bogdanović, Danica V., Dominko, Robert, Mentus, Slavko V., "Polyaniline as a charge storage material in an aqueous aluminum-based electrolyte: Can aluminum ions play the role of protons?" in Journal of Power Sources, 482 (2021):228937,
https://doi.org/10.1016/j.jpowsour.2020.228937 . .
23
6
20

Electrochemical and structural study on cycling performance of γ-LiV2O5 cathode

Milović, Miloš; Vujković, Milica; Jugović, Dragana; Mitrić, Miodrag

(2021)

TY  - JOUR
AU  - Milović, Miloš
AU  - Vujković, Milica
AU  - Jugović, Dragana
AU  - Mitrić, Miodrag
PY  - 2021
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/9148
AB  - Electrochemical and structural properties of LiV2O5 cathode were investigated. Obtained by solid state reaction at high temperature the material crystallized as gamma polymorph phase, γ-LiV2O5. The gamma structure provides two crystallographic sites to accommodate lithium ions, Li1 and Li2 position. Lithium insertion at these two sites occurs at two respective voltages versus lithium metal: ~3.6 V (Li1) and ~2.4 V (Li2). Intercalation at Li1 position is reversible in both organic and aqueous electrolyte and provides stable cycling performance at the high voltage. On the contrary, sluggish insertion/removal of Li+ at Li2 sites causes unstable performance and significant storage capacity fade at lower voltages. Lithium diffusion 3d landscape was determined by bond valence calculations applied on the γ-LiV2O5 phase, as well as on the metastable phases of γ′-V2O5 and ζ-Li2V2O5 that exist at high and low voltages respectively. The model was proposed based on inactivity of Li2 position of the metastable ζ-Li2V2O5 phase which provides explanation for the observed storage capacity loss at low voltages. © 2021 Elsevier Ltd and Techna Group S.r.l.
T2  - Ceramics International
T1  - Electrochemical and structural study on cycling performance of γ-LiV2O5 cathode
VL  - 47
IS  - 12
SP  - 17077
EP  - 17083
DO  - 10.1016/j.ceramint.2021.03.016
ER  - 
@article{
author = "Milović, Miloš and Vujković, Milica and Jugović, Dragana and Mitrić, Miodrag",
year = "2021",
abstract = "Electrochemical and structural properties of LiV2O5 cathode were investigated. Obtained by solid state reaction at high temperature the material crystallized as gamma polymorph phase, γ-LiV2O5. The gamma structure provides two crystallographic sites to accommodate lithium ions, Li1 and Li2 position. Lithium insertion at these two sites occurs at two respective voltages versus lithium metal: ~3.6 V (Li1) and ~2.4 V (Li2). Intercalation at Li1 position is reversible in both organic and aqueous electrolyte and provides stable cycling performance at the high voltage. On the contrary, sluggish insertion/removal of Li+ at Li2 sites causes unstable performance and significant storage capacity fade at lower voltages. Lithium diffusion 3d landscape was determined by bond valence calculations applied on the γ-LiV2O5 phase, as well as on the metastable phases of γ′-V2O5 and ζ-Li2V2O5 that exist at high and low voltages respectively. The model was proposed based on inactivity of Li2 position of the metastable ζ-Li2V2O5 phase which provides explanation for the observed storage capacity loss at low voltages. © 2021 Elsevier Ltd and Techna Group S.r.l.",
journal = "Ceramics International",
title = "Electrochemical and structural study on cycling performance of γ-LiV2O5 cathode",
volume = "47",
number = "12",
pages = "17077-17083",
doi = "10.1016/j.ceramint.2021.03.016"
}
Milović, M., Vujković, M., Jugović, D.,& Mitrić, M.. (2021). Electrochemical and structural study on cycling performance of γ-LiV2O5 cathode. in Ceramics International, 47(12), 17077-17083.
https://doi.org/10.1016/j.ceramint.2021.03.016
Milović M, Vujković M, Jugović D, Mitrić M. Electrochemical and structural study on cycling performance of γ-LiV2O5 cathode. in Ceramics International. 2021;47(12):17077-17083.
doi:10.1016/j.ceramint.2021.03.016 .
Milović, Miloš, Vujković, Milica, Jugović, Dragana, Mitrić, Miodrag, "Electrochemical and structural study on cycling performance of γ-LiV2O5 cathode" in Ceramics International, 47, no. 12 (2021):17077-17083,
https://doi.org/10.1016/j.ceramint.2021.03.016 . .
4
3