FUNDED BY THE SCIENCE FUND OF THE REPUBLIC OF SERBIA

Program for excellent projects of young researchers: PROMIS 2020-2022

HIGH-CAPACITY ELECTRODES FOR AQUEOUS RECHARGEABLE MULTIVALENT-ION BATTERIES AND SUPERCAPACITORS: NEXT STEP TOWARDS A HYBRID MODEL

APPROVED BUDGET CEILING IS EUR 180.689.98

MAIN GOAL:

HiSuperBat

project (06.08.2020 – 31.12.2022) was successfully completed and the planned outcomes were achieved. The project developed carbon and vanadium oxide materials for the next generation of multivalent-ion batteries and supercapacitors. A new concept for producing safe and sustainable carbon supercapacitor, based on Aluminum-ion chemistry, has been proposed and published in a high-ranking electrochemical journal such as Journal of Power Sources (IF=9.794). A new concept of aqueous battery, based on hybridization of carbon anode and calcium vanadium oxide cathode, combined with Ca-containing aqueous electrolyte, was also propounded. The performance of the constructed hybrid cell and its comparison with the commercial aqueous model will be published.

In summary, the project results, which provided a lot of fundamental and applied knowledge in the energy storage field, are published in 12 international journal papers and 19 conference announcements, with the best impact factor of 20.831. Project coordinator was invited to attend two international conferences in 2023, ”MATSUS23: #SusBat – Enabling Beyond Classical Li-ion Batteries through materials development and sustainability”, Valencia, Spain (invited speaker) https://www.nanoge.org/…/susbat-enabling-beyond… and ‘’ISNRE2023 – International summit on non-renewable and renewable energy’’, London, England (keynote speaker) https://www.spectrumconferences.com/2023/isnre .

We enjoyed doing research within this program and are looking forward to future joint collaborations

MOTIVATION:

  •  the limited lithium sources
  •  cost and safety issues of Li-ion battery due to the presence of Li, Co and organic electrolyte. 

Multivalent-ion batteries could be one of the solutions which would solve the issue of lithium, reduce the price of the battery, simplify production and make it safer. Therefore, the search for new, low cost and high safety materials, capable of storing large amount of multivalent-ions, is of great importance and HisuperBat will address these challenges.

TEAM:

  •  The HiSuperBat project has gathered researchers from three reputable institutions under the patronage of University of Belgrade, into a team which would contribute to the development of the future energy storage technology.

New team member, Maja Jović Kuzmanović from Institute of Technical Sciences of SASA, who has a great experience in the field of batteries, joined the project team (6.07.2021.-6.08.2022).

Contact: Milica Vujković (project coordinator), milica.vujkovic@ffh.bg.ac.rs; More info: www.hisuperbat.rs

EQUIPMENT:

The project also enlarged capacities/resources at partners’ organizations

Interface 1010E Potentiostat/Galvanostat GAMRY (FPC)

8 Channel Battery Analyzer- Battery testing device BST8-MA (FPC)

Precision disc Cutter with Standard 16, 19, 20 Dia. Cutting Die & 3 – 24mm MSK-T-10, (FPC).

Digital pressure Crimper MSK-160 E (FPC)

DXR 780 nm  High Brightness Exc for Raman device (FPC)

DXR Fiber Probe Customer Align for Raman device (FPC)

Interface 1010E Potentiostat/Galvanostat GAMRY (ITS SASA)

Split Test Cell with Beryllium (Be) Window for In-situ XRD Analysis of Battery Electrode – EQ-STC-BEW (ITS SASA)

Electrochemical glass cell (5-70 mL) with titration vessel lid with 5 oppening (ITS SASA)

Quartz tube (INV)

Small facilities including reference eletrodes, glass carbon and ITO supporting electrodes, current colectors, desiccator, tools for the synthesis methods, chemicals, etc. (FPC, INV, ITS SASA) .  

MAIN PROJECT OUTCOMES:

New type of safe and sustainable Al-based carbon aqueous supercapacitor

New concepts for increasing charge storage properties of carbon and vanadium oxides based on mixing of electrolyte ions

New fundamental knowledge regarding vanadium oxides and carbon chemistry

Design of Ca-based hybrid cell combining carbon and vanadium oxide

TEAM BUILDING

Visit to ” ElevenEs” Company in Subtica, which aims to develop and produce Li-ion batteries.

CONFERENCE ORGANIZATION (COIN2022)

The International Symposium “Contemporary batteries and supercapacitors” – COIN2022 was held at the Serbian Academy of Sciences and Arts in Belgrade on June 1-2, 2022, (www.coin2022.org). The Faculty of Physical Chemistry, co-organized this symposium, together with the National Institute of Chemistry in Ljubljana, the Faculty of Metallurgy and Technology, University of Montenegro and the Serbian Academy of Sciences and Arts. COIN2022 was supported by the Science Fund of the Republic of Serbia, NATO Science for Peace and Security programme and The Serbian Academy of Sciences and Arts.

Plenary speakers were European leaders in batteries &supercapacitors: prof. Christian Masquelier, University of Picardy Jules Verne & CNRS, prof. Patrice Simone, University of Toulouse III – Paul Sabatier, Robert Dominko, National Institute of Chemistry, Ljubljana (the first day), Prof. Kristina Edstrom, Uppsala University, Dr. Isidora Cekić-Lasković, Helmholtz-Institute Münster (HI MS) and Dr. Nagore Ortiz-Vitoriano, CIC EnergiGUNE (the second day), also shared their research activities in this field. Professors and researchers from the region also presented their research at the Symposium and the special attention was drawn to the presentation of the project regarding the construction of the first gigafactory for Li-ion batteries production in Europe, (ElevenEs company in Subtica).

Our principal investigator, Dr. Milica Vujković, the organizing committee member, gave a lecture on the topic “Towards Alternative Li-free Electrode Materials: Synthesis and Phase Composition Interrelation”, while our participants, Dr. Nikola Zdolšek, Dr. Milica Vasić and MSc Dušan Mladenović participated in the symposum with the poster presentations of “Enhancement of Supercapacitors Energy Density Using Manganese Modified Carbon Electrode and Mixture of Multivalent Ions Electrolyte”, “A Series of Magnesium Vanadium Oxide Materials Potentially Applicable for Aqueous RMBs” and “Cyclic Stability of Sodium-pillared Vanadium Oxides-carbon Composite in Aqueous Electrolytes”, respectively.

PROJECT PROMOTION, PUBLICITY AND VISIBILITY:

https://klima101.rs/author/milica-vujkovic/

https://www.energetskiportal.rs/wp-content/uploads/2021/04/MEP21-link.pdf

https://www.rts.rs/page/radio/sr/story/24/radio-beograd-2/4324339/baterije-bez-litijuma.html

https://www.rts.rs/page/radio/sr/story/23/radio-beograd-1/4330342

https://www.politika.rs/sr/clanak/479615/Srpski-naucnici-u-potrazi-za-superbaterijom

https://www.blic.rs/

https://www.politika.rs/sr/clanak/496553/Nauka-u-orbiti-fantastike-i-biznisa

https://www.novosti.rs/c/ekonomija/vesti/1183355/nas-kalcit-bolji-litijuma-dve-lokacije-jugoistoku-srbije-pronadjena-velika-nalazista-plemenitog-metala-minerala-kalcijuma

https://n1info.rs/zeleni-kutak/dokle-je-srbija-stigla-u-radu-na-baterijama-koje-ne-stete-prirodi/

Journal papers

  1. Dragana Jugović, Miloš D Milović, Tanja Barudžija, Maja Kuzmanović, Milica Vujković, Miodrag Mitrić, The Influence of a Binder in a Composite Electrode: The Case Study of Vanadyl Phosphate in Aqueous Electrolyte, Materials 202215(24), 9041. https://doi.org/10.3390/ma15249041

2. Nikola Zdolšek, Bojan Janković, Miloš Milović, Snežana Brković, Jugoslav Krstić, Ivana Perović, Milica Vujković, Deep Eutectic Solvent (DES) for In Situ Templating Carbon Material: Carbon Characterization and Application in Supercapacitors Containing Multivalent Ions, Batteries 2022, 8(12), 284. https://doi.org/10.3390/batteries8120284

3. Nikola Zdolšek, Ivana Perović, Snežana Brković, Gvozden Tasić, Miloš Milović, Milica Vujković, Deep Eutectic Solvent for Facile Synthesis of Mn3O4@N-Doped Carbon for Aqueous Multivalent-Based Supercapacitors: New Concept for Increasing Capacitance and Operating Voltage, Materials 2022, 15(23), 8540. https://doi.org/10.3390/ma15238540

4. Ljiljana Veselinović, Miodrag Mitrić, Lidija Mančić,Paula M. Jardim, Srečo Davor Škapin ,Nikola Cvjetićanin, Miloš D. Milović, Smilja Marković, Crystal Structure and Electrical Properties of Ruthenium-Substituted Calcium Copper Titanate, Materials 2022, 15(23), 8500.

5. Milica M Vasić, Miloš Milović, Danica Bajuk–Bogdanović, Tamara Petrović, Milica J Vujković*, Simply Prepared Magnesium Vanadium Oxides as Cathode Materials for Rechargeable Aqueous Magnesium Ion Batteries, Nanomaterials 2022, 12, 2767. https://doi.org/10.3390/nano12162767.

6. Milica J Vujković*, Dušan Mladenović, Miloš Milović, Tamara Petrović, Danica Bajuk – Bogdanović, Biljana Šljukić – Paunković, Slavko Mentus, Sodium-pillared vanadium oxides as next-gen materials: Does co-inserted water control the cyclic stability of vanadates in an aqueous electrolyte? Electrochimica Acta, 425 2022, 140603,  https://doi.org/10.1016/j.electacta.2022.140603

7. Aleksandra Gezović, Jana Mišurović, Branislav Milovanović, Mihajlo Etinski, Jugoslav Krstić, Veselinka Grudić, Robert Dominko, Slavko Mentus, Milica Vujković*, High Al-ion storage of vine shoots-derived activated carbon: New concept for affordable and sustainable supercapacitors, Journal of power sources, 538 (2022) 231561.  https://doi.org/10.1016/j.jpowsour.2022.231561

8. Nikola Zdolšek, Milica Vujković, Snežana Brković, Ana Jocić, Tatjana Trtić-Petrović, Aleksandra Dimitrijević , Biljana Šljukić – Paunković*, Boosting electrocatalysis of oxygen reduction and evolution reactions with cost-effective cobalt and nitrogen doped carbons prepared by simple carbonization of ionic liquids, International Journal of Hydrogen Energy, 47 (2022), 14847. https://doi.org/10.1016/j.ijhydene.2022.02.225

9. Miloš Milović, Milica Vujković, Dragana Jugović, Miodrag Mitrić, “Electrochemical and structural study on cycling performance of γ-LiV2O5 cathode” Ceramics International, (2021):17077-17083, Ceramic International, 47, 2021, 17077-17083  https://www.sciencedirect.com/science/article/pii/S0272884221006799

10. Gezović#, M. J. Vujković#,*, M. Milović, V. Grudić, R. Dominko, S. Mentus, Recent developments of Na4M3(PO4)2(P2O7) as the cathode material for alkaline-ion rechargeable batteries: challenges and outlook” , Energy Storage Materials, 37 (2021) 243-273. #equal first autor https://www.sciencedirect.com/science/article/pii/S2405829721000544.

11. M. J Vujković*, M. Etinski, B. Vasić, B. Kuzmanović, D. Bajuk-Bogdanović, R. Dominko, S. Mentus, J. Power Sources, 482, 2021, 228937. https://www.sciencedirect.com/science/article/pii/S0378775320312374.

12. Bojan Janković, Nebojša Manić, Ivana Perović, Milica Vujković, Nikola Zdolšek, 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), Journal of Molecular Liquids, 374, 2023, 121274 https://doi.org/10.1016/j.molliq.2023.121274

Conference papers:

[1] Tamara Petrović, Miloš Milović, Jana Mišurović, Aleksandra Gezović, Veselinka Grudić, Milica Vujković, Hybrid aqueous Ca-ion battery: Design and Performance,Twentieth Young Researchers’ Conference Materials Science and Engineering, Programme and the Book of Abstracts, November 30-December 2, 2022, Belgrade, Serbia, p.67. [2] Dragana Jugović, Miloš Milović, Tanja Barudžija, Miodrag Mitrić, Vanadyl phosphate as a host material for aluminium intercalation, 6th Int. Symposium on Materials for Energy Storage and Conversion mESC-IS 2022, p.45. [3] Milica J. Vujković, Aqueous multivalent-ion chemistry of vanadium oxides: Novelties and Challenges, Twenty-third annual conference- Yucomat 2022, Herceg Novi, Monenegro, Serbia Program and the Book of Abstracts ISBN 978-86-919111-7-1 p. 79. [4] Jana Mišurović, Aleksandra Gezović, Jugoslav Krstić, Branislav Milovanović, Veselinka Grudić, Slavko Mentus, Milica Vujković, Comparative study of biomass-derived carbon interfacial processes in Aluminum-based and conventional acidic electrolyte, Twenty-third annual conference – Yucomat 2022, Herceg Novi, Monenegro, Serbia Program and the Book of Abstracts ISBN 978-86-919111-7-1 p. 91. [5] Milica Vujković, Tamara Petrović, Dušan Mladenović, Miloš Milović, Danica Bajuk- Bogdanović, Biljana Šljukić-Paunković, Slavko Mentus, Sodium-pillared vanadium oxide decorated with carbon particles as electrode material for more sustainable energy storage of the future, Second International Conference on Electron Microscopy of Nanostructures – Elmina 2022, August 22nd–26th, 2022, Belgrade, Serbia Program and the Book of Abstracts p. 172-173.

[6] N Zdolšek, Nova generacija baterija i superkondezatora: Korak ka hibridnom modelu,  https://ridibf.rs/en/news, project presentation, 2022.

[7] Milica J. Vujković, Aleksandra Gezović, Danica Bajuk-Bogdanović, Veselinka Grudić, Slavko Mentus, Towards alternative Li-free Electrode Materials: Synthesis and Phase Composition Interrelation, COIN2022, June 1-2, 2022, Serbian Academy of Sciences and Arts, Belgrade, Serbia, Program and the Book of Abstracts, ISBN 978-86-82139-86-7, p.14. [8] Tamara Petrović, Danica Bajuk-Bogdanović, Milica Vujković, Layered CaV2O6 as Promising Electrode Material for Aqueous Calcium-ion Batteries COIN2022, June 1-2, 2022, Serbian Academy of Sciences and Arts, Belgrade, Serbia, Program and Book of Abstracts, ISBN 978-86-82139-86-7, p.29. [9] D. Mladenović, T. Petrović, D. Bajuk-Bogdanović, B. Šljukić Paunković, S. Mentus, M. Vujković, Cyclic Stability of Sodium-pillared Vanadium Oxides-carbon Composite in Aqueous Electrolytes, , COIN2022, June 1-2, 2022, Belgrade, Program and Book of Abstracts, ISBN 978-86-82139-86-7p. 31.  [10] Nikola Zdolšek, Ivana Perović, Snežana Brković, Mina Seović, Slavko Dimović and Milica Vujković, Enhancement of Supercapacitors Energy Density Using Manganese Modified Carbon Electrode and Mixture of Multivalent Ions Electrolyte, COIN2022, June 1-2, 2022, Serbian Academy of Sciences and Arts, Belgrade, Serbi, Program and Book of Abstracts ISBN 978-86-82139-86-7 p.34. [11] Aleksandra Gezović, Jana Mišurović, Jugoslav Krstić, Nikola Simović, Veselinka Grudić, Robert Dominko, Slavko Mentus, Milica J. Vujković, Al-ion Charge Storage Ability of Vine Shoots-derived Carbon, COIN2022, June 1-2, 2022, Serbian Academy of Sciences and Arts, Belgrade, Serbia, ISBN 978-86-82139-86-7, Program and Book of Abstracts, p. 35. [12] Milica M. Vasić, Milica Vujković, A Series of Magnesium Vanadium Oxide Materials Potentially Applicable for Aqueous RMBs, COIN2022, June 1-2, 2022, Serbian Academy of Sciences and Arts, Belgrade, Serbia, Program and Book of Abstracts ISBN 978-86-82139-86-7, p.45. [13] Branislav Milanović, Milica Vujković, Mihajlo Etinski, Al3+ Cation Interaction with Pristine and Defective Graphene Using Microsolvated Cluster Model: DFT Study  COIN2022, June 1-2, 2022, Serbian Academy of Sciences and Arts, Belgrade, Serbia, Program and Book of Abstracts,  p. 48. [14] N. Zdolšek, S. Brković, I. Perović, M. Ćurčić, S. Dimović, M. Vujković, “NEW GENERATION OFELECTROCHEMICAL SUPERCAPACITORS”, EcoTER’22, 21-24 June 2022, Hotel Sunce, Sokobanja, Serbia,Proceedings, pp 436-440. [15] D. Mladenović*, M. Milović, B. Šljukić, S. Mentus, M.Vujković, “Sodium-vanadium oxide carbon as next-gen anode material for alkaline-ion aqueous rechargeable batteries” (ise213853), 72nd Annual Meeting of the International Society of Electrochemistry in Jeju Island, Korea, from 29 August – 3 September 2021, in a hybrid form (pre-recorded online poster presentation); https://annual72.ise-online.org/  (ISE213853) [16] M. Milović, M. Vujković, D.J ugović, M.Mitrić, Structural and electrochemical properties of gamma LiV2O5 cathode, Serbian Ceramic Society Conference, Belgrade 20-21. September 2021, Book of the Abstract page 84. https://dais.sanu.ac.rs/handle/123456789/11896. [17] N. Zdolšek*, I. Perović, S. Brković, M. Vujković, Aqueous Multivalent-Ions Electrolyte for Electrochemical Supercapacitors: Boosting Electrochemical Performances, 21st European Meeting on Environmental Chemistry November 30 – December 3, 2021, Novi Sad, Serbia. https://emec21.rs/programme. [18] M.M. Vasić, M. Milović, D. Bajuk- Bogdanović , Milica Vujković, Simply prepared Mg-V-O as potential cathode material for rechargeable aqueous magnesium ion batteries, Nineteenth Young Researchers Conference – Materials Science and Engineering December 1-3, 2021, Belgrade, Serbia, p.22.  https://www.mrs-serbia.org.rs/index.php/book-of-abstracts. [19] T. Petrović, M. Milović, D.Bajuk-Bogdanović, Milica Vujković, Layered CaV2O6  as promising electrode material for multivalent storage, Nineteenth Young Researchers Conference – Materials Science and Engineering December 1-3, 2021, Belgrade, Serbia, p.53. https://www.mrs-serbia.org.rs/index.php/book-of-abstracts.
 

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