Development of doped vanadium oxide/graphene composites for ultra-performance batteries and supercapacitors by physical vapour deposition for sustainable and eco-friendly energy storage applications (VANABATSUP)
Project Director: Dr. Tite Martial Teddy
- CO - National Institute of Research and Development in Materials Physics (INCDFM), Magurele;
- P1 - National Institute of Research and Development for Cryogenic and Isotopic Technologies (ICSI), Râmnicu Vâlcea.
Energy storage plays an important role in the modern world. One of the main trends that drive energy storage development is the rise of electrical devices (e.g., smart phones, smart watches, e-books, smart keys), internet of Things (IoT) in our daily life. Despite their great success, lithium ion batteries (LIBs) still need improvements in energy density, fast charge capabilities, cyclic durability and cost. LIBs are not fully safe in certain conditions and the commercial failure of Samsung Galaxy Note 7 in 2016 is an incontestable example. Extensive efforts have been devoted to either improve LiBs by replacing the commercial cathode (e.g., LiCoO2) or by designing new batteries without Lithium (Li) (e.g., Al, Mg, Na, Zn batteries) responding to the concern about the limited Li resource. New devices are required to be more sustainable and greener with respect to our environment. In this context, vanadium oxides, graphene and their related compounds are nowadays the most appealing materials for applications in energy harvesting.
VANABATSUP project intends to synthesize, test and develop advanced batteries or super capacitors based on doped vanadium oxide/graphene composites as sustainable, eco-friendly and ultra-performance storage resources. Despite their good promises, the commercialization of hybrids vanadium oxides-graphene based composites is hampered by various obstacles including fastidious synthesis methods, including the current use of graphene oxide which can lose its efficiency due to a tendency to aggregate. Recently, the project leader has demonstrated not only the possibility to synthesis few layers of graphene by physical vapor deposition (PVD) method, but also shown their applicability as electrochemical devices. A recent review underlined that those graphene layers have not yet been tested for energy storage application. Therefore, VANABATSUP intends to fill this gap and aims to propose alternative cathodes for energy storage application.
The project falls starts from a technology readiness level 2 (TRL2) and aims to reach in the framework of a collaborative work (between INCDFM, ROM-Est - Laboratory for research in energy storage technologies, and ICSI) to TRL3 stage, materialized in a functional battery or supercapacitor (e.g., coin or pouch cells).
General objectives: (i) synthesis by PVD techniques of innovative hybrid materials based on undoped and doped vanadium dioxide and graphene composites and; (ii) investigation of their applicability in energy storage as batteries (e.g., Li+, Na+, Mg2+, Zn2+) or supercapacitors.
Specific objectives (OS):
- OS1: Synthesis. Undoped and doped vanadium oxides and their hybrid architectures will be synthesized by PVD methods. Since these techniques are entailing different physical processes, they will allow to obtain films with various properties. Identification of optimal thin films fabrication protocols.
- OS2: Characterization and materials selection. Preliminary physical-chemical investigations will be performed (for instance by X-ray diffraction) to probe the single or multi-phase oxide nature of the films. Further characterizations (e.g., optical microscopy, AFM, SEM, EDS, optical measurements, XPS) will be performed to understand the materials properties in conjunction with OS3.
- OS3: Fabrication of electrodes and electrochemical characterization. Evaluation of electrochemical performance in aqueous electrolytes by cyclic voltammetry (CV), impedance (EIS) and galvanostatic static charge discharge (GCD) measurements will be carried out with a conventional three-electrode system. Selection of best materials in conjunction with OS2.
- OS4: From Lab-to-Fab. Development, evaluation and validation of the device technology (e.g., coin cells and pouch cells) in collaboration with ROM-Est and ICSI. Evaluation of the large scale electrode synthesized by magnetron sputtering, an industrial capable technique.
The project activities are grouped in 5 work packages (WP):
WP2. Synthesis of vanadium oxides, graphene and their hybrids structure by PVD.
WP3. In-depth characterization of the physical-chemical properties.
WP4.Evaluation of electrochemical properties.
WP5. From lab-to-fab: from materials to the fabrication of batteries and supercapacitors.
CO - National Institute of Research and Development in Materials Physics, Magurele
|No./crt.||Name SURNAME||FUNCTION||PROJECT ROLE|
|1||Teddy TITE||Senior researcher II||Director of PED project|
|2||George STAN||Senior researcher I||Research team member|
|3||Elena MATEI||Senior researcher I||Research team member|
|4||Constantin-Cătălin NEGRILĂ||Senior researcher II||Research team member|
|5||Mihaela BAIBARAC||Senior researcher I||Research team member|
|6||Maria-Cristina BARTHA||Senior researcher III||Research team member|
P1 - National Institute of Research and Development for Cryogenic and Isotopic Technologies, Râmnicu Vâlcea
|No./crt.||Name SURNAME||FUNCTION||PROJECT ROLE|
|1||Mihaela-Ramona BUGA||Senior researcher I||Responsible of Partner 1|
|2||Adnana ZAULET||Senior researcher III||Research team member|
|3||Cosmin UNGUREANU||PhD student||Research team member|
Summary of Stage I/2020:
The first stage of the 472PED/2020 project was primarily focused on (i) a preliminary study concerning the synthesis of vanadium oxide-based (VOx) materials and (ii) the setting up of a benchtop equipment dedicated to electrochemical measurements (i.e., a Potensiostat/Galvanostat system, purchased in the framework of 472PED). Furthermore, new working electrode holders have been fabricated and were found adequate for performing electrochemical measurements on metallic current collectors. Supplemental, a V2O5 target has been fabricated by spark plasma sintering, and used to synthesize the first series of vanadium oxide-based thin films by the pulsed laser deposition (PLD) technology, which were subsequently converted by thermal annealing (with the help of a lab-made rapid thermal annealing system) to the V2O5 phase.
Results delivered at the end of Stage I/2020:
- 1 preliminary scientific study on the synthesis and characterization of the VOx-based materials;
- 1 physical object: a preliminarily-defined material based on VOx;
- 1 experimental set for electrochemical measurements.
Summary of Stage II/2021:
The second stage of execution targeted the synthesis and characterization of undoped and doped vanadium oxide directly on the current collector, as well as the investigation of their integration with others materials such as graphene. Based on the physical-chemical analyses and the in-situ electrochemical characterization, a selection of the most promising materials was accomplished, which, in the final stage of the project (2022), will be integrated and tested in delineated prototypes. We have demonstrated the possibility to reduce VOx by thermal annealing in nitrogen at low pressure to form either a predominant VO2(B) phase on aluminum foil or rhombohedral V2O3 phase on graphene foil. Furthermore, we have also shown the possibility to functionalize VOx thin films deposited on graphene with ZnO micro-sheets and nano-rods after electrodeposition. Both partner institutions (i.e., INCDFM and ICSI) adopted its own measures to perform electrochemical tests on the electrodes. Samples have been self-assembled in coin cells. The testing was performed at the same temperature and humidity conditions for all samples. The results indicated that VO2(B) samples show the best electrochemical performance. The C/20 capacity obtained for the first cycle in the case of this type of sample, compared to the theoretical capacity, was 57%, which is mainly explained by the intercalation/deintercalation of Li+ during discharge/charge cycles.
Results delivered at the end of Stage II/2021:
- 1 scientific study on the influence of doping, morphology, defects and crystal order and interfaces on the functional response and electrochemical properties of materials of interest;
- 2 physical objects: 1 functional material and 1 working electrode;
- 1 optimized synthesis method;
- 3 scientific communications at international conferences;
- 1 article published in a Web of Science® indexed journal with impact factor, situated in the Q2 quartile.
The scientific report cannot be yet divulged on the project website, as the results are in the process of being published, but it can be accessed upon request at UEFISCDI.
2020-2021: THE joint SYNTHETIC SCIENTIFIC REPORT corresponding to Stages I+II, in .pdf format, is available at UEFISCDI, and can be accessed by request.
2021: Hajar GHANNAM, ABDELMALEK ESSAADI UNIVERSITY, MOROCCO, performed in the period September – December 2021, a scientific work stage in the field of synthesis, characterization, and integration of oxide materials in battery devices, under the coordination of Dr. Teddy TITE (Project director of 472 PED/2020).
Web of Science® articles - published or accepted:
- 01. A. Gaddam*, A.A. Allu, S. Ganisetti, H.R. Fernandes, G.E. Stan^, C.C. Negrila^, A.P. Jamale, F. Mear, L. Montagne, J.M.F. Ferreira*; Effect of vanadium oxide on the structure and Li-Ion conductivity of lithium silicate glasses; J PHYS CHEM C 125 (2021) 16843. https://doi.org/10.1021/acs.jpcc.1c05059
- 01. T. Tite^,*, M. Buga^, C. Ungureanu^, A.A. Zaulet^, I. Stavarache, E. Matei^, G.E. Stan^, C.C. Negrila^, A.C. Galca, M.C. Bartha^, M. Baibarac^; Synthesis of vanadium oxide/graphene thin films by physical vapor deposition method for high performance batteries, E-MRS 2021 Fall Meeting, Symposium B: „Battery and Energy Storage Devices: From Materials to Eco-Design”, 20–23 September 2021, online (poster presentation).
- 02. T. Tite^,*, H. Ghannam, M. Buga^, C. Ungureanu^, A.A. Zaulet^, I. Stavarache, E. Matei^, G.E. Stan^, C.C. Negrila^, A.C. Galca, M.C. Bartha^, M. Baibarac^; Doped vanadium oxide films by physical vapour deposition method for energy storage application, 23rd International Conference “New Cryogenic and Isotope Technologies for Energy and Environment” EnergEn 2021, Băile Govora, Romania, 26–29 October 2021, online (oral presentation).
- 03. H. Ghannam*, T. Tite^,*, A. Chahboun, M. Buga^, C. Ungureanu^, A.A. Zaulet^, A.C. Galca, M.Y. Zaki, E. Matei^, I. Stavarache, C.C. Negrila^, G.E. Stan^, M.C. Bartha^, M. Baibarac^; Advanced electrode based on zinc oxide-graphene for sodium-ion battery: Influence of morphology and doping, 23rd International Conference “New Cryogenic and Isotope Technologies for Energy and Environment” EnergEn 2021, Băile Govora, Romania, 26–29 October 2021, online (poster presentation).
^project team member
Teddy TITE, PhD in Materials Science
Senior Researcher II
Telephone: +40-(0)21-2418 131
Department: Laboratory of Multifunctional Materials and Structures
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