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. Teddy TITE

Project ID: PN-III-P2-2.1-PED-2019-4519

Project Director:  Dr. Teddy TITE

Project Type: National

Project Program: PED

Funded by: Romanian Ministry of Education and Research (CNCS - UEFISCDI)

Contractor:  National Institute of Materials Physics (INCDFM)

Project Status:  Finished

Start Date: 23 October, 2020

End Date: 22 October, 2022



  • 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.

Project summary:

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):

WP1. Management.

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

1Teddy TITESenior researcher IIDirector of PED project
2George STANSenior researcher IResearch team member
3Elena MATEISenior researcher IResearch team member
4Constantin-Cătălin NEGRILĂSenior researcher IIResearch team member
5Mihaela BAIBARACSenior researcher IResearch team member
6Maria-Cristina BARTHASenior researcher IIIResearch team member
7Anna STEPANOVAAssistant researcherResearch team member


P1 - National Institute of Research and Development for Cryogenic and Isotopic Technologies, Râmnicu Vâlcea

1Mihaela-Ramona BUGASenior researcher IResponsible of Partner 1
2Adnana ZAULETSenior researcher IIIResearch team member
3Cosmin UNGUREANUPhD studentResearch 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.


Summary of Stage III/2022:

In the 3rd Stage of the project, vanadium oxide (VOx) thin films and compounds have been prepared by various deposition methods (e.g., pulsed laser ablation (PLD); magnetron sputtering; electrochemistry), in full agreement with the implementation plan. Their applicability as energy storage devices, such as lithium ion battery (LiBs), has been investigated. The physico-chemical properties of the samples have been unveiled by using an array of advanced characterization methods.

In continuation of the progresses achieved in the 2nd Stage of the project (2021), new batches of undoped and doped vanadium oxide films have been synthesized by PLD and deposited either on aluminium (Al) or on graphene/aluminium foil (G/Al). The results have confirmed the possibility to reproducibly obtain the VO2(B) polymorph phase on Al and the V2O3 phase on G/Al; these two phases being the most promising for LiBs, amongst all vanadium oxide phases, possessing theoretical capacities as cathodes of 322 mAhg-1 and 356 mAhg-1, respectively. Selected samples have been tested as CR 2032-type coin cells prototypes for LiBs. Unfortunately, despite the efforts and a clear observation of Li intercalation/desintercalation, the capacity of VO2(B) on Al foil from ALL FOILS company (thickness 38 mm) was found to be quite mitigated with a first capacity of only 62 mAhg‑1; those results contrasted to those obtained on the Al foil from MTI corporation (i.e., 161 mAhg-1), and suggest an electrochemical dependence of the Al foil used. Furthermore, important capacity fading was also observed after 200 cycles, with the capacity declining to 2 mAhg-1. The electrochemical performance of batches of V2O3 deposited on G/Al was found better with an initial capacity of 300 mAhg-1. Furthermore, we observed that a 5 mol% Sn-doping in V2O3 can improve the electrochemical performance (i.e., loss of only 0.128% per cycle during a long cycle stability test of 200 cycles), notably concerning the cycling stability. This can be owned to Sn, causing an expansion of V2O3 lattice which reduces the electrochemical reaction resistance, improving the reversibility of electrochemical processes. The innovative methodology to obtain VO2(B) directly on Al foil has been included into a patent application submitted to OSIM, while the results obtained on G/Al will be disseminated through a scientific article (in this respect a manuscript has been submitted to Electrochimica Acta, a Q1 Web of Science®-indexed journal). In the same direction, we have also explored the possibility to obtain the VO2(B) phase on another current collector (i.e., nickel). By using a different annealing protocol, we have obtained the desired phase in both undoped and Sn-doped phases form. However, non-reproducibility occurrences were also met, even if striving to apply identical preparation and post-processing conditions.

In the framework of this 3rd Stage of the project, further significant efforts have been devoted to delineate deposition protocols for larger area applications. One drawback of the PLD method is that the size of the sample is limited to less than 20 mm, which hampers its large-scale applicability to ESDs (pouch cells included). Also, the mass of the active materials generally does not exceed few hundreds of micrograms, which could limit the energy density as battery devices. For this purpose, in accordance to the tasks defined in the 3rd Stage of the project, other deposition techniques have been explored, such as radio-frequency magnetron sputtering (RF-MS). Batches of thin films have been synthesized by RF-MS in inert (pure argon (Ar)) and in reactive (5 vol% O2 + 95 vol% Ar) working atmosphere by using a target made of V2O5 powder. By designed RTA treatments was made possible to obtain the VO2(B) phase at 480 °C for the samples without oxygen, but the results were rather dependent on the film thickness. Importantly, we found that it is also possible to obtain by RF-MS directly a crystalline V2O5 phase for as-deposited film prepared under a reactive (oxygen containing) working gas ambient. Thereby, we have decided to use this advantage to the benefit of pouch cells fabrication. Furthermore, other alternative deposition methods have been explored, in the pursuit to obtain either VO2(B) or V2O3 phase son larger surface area substrates. In this respect, the (i) electrochemical; (ii) hydrothermal approach; and (iii) spray coating methods have been approached. Several innovative aspects emerged during our researches, as it will be described hereafter. Briefly, we have been able to obtain: a V2O3 phase on Ni foam; a VO2(B) phase in a controlled way by hydrothermal treatment; and established an extremely cheap V2O5 spray-coating-based deposition solution without evidences of precipitation. Some samples prepared by spray coating have been used to fabricate pouch cells in the framework of this project.

Results delivered at the end of Stage III/2022:

  • 1 scientific study on the electrochemical properties of the PVD-deposited films;
  • 1 scientific study on the reversibility, charge-discharge and cycling of devices;
  • Physical objects: 1 material with reproducible electrochemical response, 1 working-electrode; 1 energy storage device (pouch cell);
  • 1 manuscript submitted to a Web of Science®-indexed journal with impact factor, situated in the Q1 quartile;
  • 1 OSIM patent request;
  • 3 communications to conferences with international participation.

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.

2022: THE SYNTHETIC SCIENTIFIC REPORT corresponding to Stage III, 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 submitted:

  • 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 glassesJ PHYS CHEM C 125 (2021) 16843.
  • 02. C. Ungureanu^, T. Tite^,*, M. Buga^,*, I. Stavarache, E. Matei^, C.C. Negrila^, A.C. Galca, A.A. Zaulet^, L. Trupina; Pulsed laser deposited vanadium sesquioxide thin films on graphene/aluminium foil for battery applications; submitted to ELECTROCHIM ACTA (2022).

OSIM Patent request:

  • 01. T. Tite^, I. Stavarache, A. Galatanu, M. Lazar, C. Negrila^, M. Buga^, C.G. Ungureanu^, A.A. Spinu-Zaulet^; Binder-free vanadium dioxide VO2(B) thin films obtained directly on aluminium foil by pulsed laser deposition as battery cathode and method of preparation thereof; OSIM patent request no. A/00665/2022.

International conferences:

  • 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”, 20th–23rd 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, 26th–29th 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, 26th–29th October 2021, online (poster presentation).
  • 04. T. Tite^,*, H. Ghannam, C. Ungureanu^, M. Buga^, A.A. Zaulet^, I. Stavarache, O. El Khouja, E. Matei^, G.E. Stan^, M.Y. Zaki, C.C. Negrila^, A. Galatanu, A.C. Galca, M.C. Bartha^, M. Baibarac^, A. Chahboun; Vanadium oxides/zinc oxide thin films for energy storage applications: Study of their combination and synergy with graphene; E-MRS 2022 Spring Meeting, Symposium J: “Future electrochemical energy storage materials: From nanoscience to device integration and real environment application”, March 30th–June 3rd 2022, online (oral presentation).
  • 05. H. Ghannam*, O. El Khouja, C. Ungureanu^, T. Tite^, M. Buga^, A.A. Zaulet^, E. Matei^, C.C. Negrila^, G.E. Stan^, A.C. Galca, A. Chahboun; Porous cobalt oxides nanostructures electrodeposited on graphene electrode for energy storage applications; E-MRS 2022 Spring Meeting, Symposium J: “Future electrochemical energy storage materials: From nanoscience to device integration and real environment application”, March 30th–June 3rd 2022, online (poster presentation).
  • 06. T. Tite^,*, C.G. Ungureanu^, M. Buga^ , H. Ghannam, O. El Khouja, A.A. Zaulet^, I. Stavarache, E. Matei^, G.E. Stan^, C. C. Negrila^, M.C. Bartha^, A.C. Galca, A. Galatanu, M.Y. Zaki, M. Baibarac^; Vanadium oxides thin films by physical vapor deposition and electrodeposition for energy storage applications, 20th International Balkan Workshop on Applied Physics and Materials Science, July 12th–15th 2022, Constanta, Romania (poster presentation).

*corresponding/presenting author

^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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