The research of the group is essentially devoted to employ nanostructured materials and nanotechnologies in the fabrication of laboratory prototypes for energy harvesting and storage devices, also in flexible, wire-shaped or floating architectures for advanced and innovative applications. The principal subjects under study are: dye sensitized solar cells, supercapacitors, hybrid devices for harvesting and storage, microbial fuel cells.

Microbial Fuel Cells

Microbial fuel cells (MFCs) directly convert the chemical energy embedded in organic matter into electricity by exploiting the great potential of exoelectrogenic bacteria. Our research activity focuses on the optimization of efficient anodes to support the growth and proliferation of active biofilms, favouring optimal charge transfer at the interface between the biocatalyst and the anode itself. Oxygen is preferentially used as the final electron acceptor at the cathode and the design of green and sustainable catalysts for the Oxygen Reduction Reaction (ORR) is another key goal of our activity.

Even if MFCs can be accounted among the technologies available to harvest environmental energy, they are bioreactors, in which a complex set of chemical, biochemical and electrochemical reactions have to occur to allow energy conversion. Multiphysics modelling is a potent tool to drive the design of the reactors and we couple it to 3D printing technology for fast fabrication of prototypes.

Our aim is to investigate portable systems that can be directly used in real environments, especially to power sensors. For this goal we are especially investigating the use of biofilms at the anode obtained from environmental inoculum.

Contact Information

Giulia Massaglia (giulia.massaglia@polito.it)

Marzia Quaglio (marzia.quaglio@polito.it)

Eve Verpoorten (eve.verpoorten@polito.it)

Collaborations

Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia

Dye Sensitized Solar Cells (DSSC)

The standard DSSC fabrication procedure, based on sintered nanostructured TiO2 electrodes deposited by screen printing or tape casting on FTO/glass substrates, is available. Moreover, a novel microfluidic architecture has been specifically designed for the fabrication of small laboratory test-cells with a high degree of reproducibility and good capability of assembly and disassembly.

Fig.1 – DSSC prototypes in microfluidic and standard architecture and comparison of PV performance

Advanced electrodes (based on different nanostructured materials such as coral-shaped ZnO, ZnO nanoflowers, TiO2 nanotubes, graphene nanosheets…), innovative electrolyte (both in liquid, gel and or quasi-solid form) and new organic dyes have been tested. (Llink alla sezione materiali?)

Atomistic calculations are performed for a successful modelling of the surfaces and interfaces within the cell and a deeper comprehension of the light harvesting and charge transfer mechanisms.

Fig. 2 – Hemisquaraine organic dye CT1: surface charge density associated with HOMO and LUMO states for the isolated CT1 molecule, and for CT1 on ZnO and anatase TiO2 substrates

Flexible and semitransparent DSSCs have been obtained by means of an innovative combination of electrodes –with vertically aligned TiO2 nanotubes grown onto bendable titanium mesh- and photocurable polymer electrolyte membrane.

Floating and flexible photovoltaic devices are fabricated employing light-cured polymer-based DSSC s with a super-hydrophobic architecture on the external side, obtaining conversion efficiencies up to 5% and stable performance upon long-term aging tests.

Fig. 3 – Flexible DSSC (left), super-hydrophobic nano pillared array on PDMS for floating PV (right)

Contact information

Stefano Bianco
stefano.bianco@polito.it

Giancarlo Cicero
giancarlo.cicero@polito.it

Andrea Lamberti
andrea.lamberti@polito.it

Elena Tresso
elena.tresso@polito.it

Supercapacitors (SCs)

With the aim to increase the SC energy density without losing the high power density and to reduce the manufacturing cost, while keeping a good operation window, different kinds of nanostructured carbon-based electrodes are under study. The principally employed active materials are graphite powder and carbon black, glassy carbon, carbon nanotubes and, in particular, innovative 3D-graphene networks, such as graphene-based aerogels and Laser-Induced Graphene (LIG).

Moreover, depending on the desired application, different electrolyte materials, from aqueous to polymeric to ionic-liquid based and different substrates, from rigid to flexible to fiber-shaped are employed.

Fig. 1 – SCs prototypes fabricated in coin cell (left) and in wounded (right) architectures

Laboratory prototypes are fabricated both in standard planar (irreversibly sealed with thermoplastic polymer) microfluidic (for a reversible sealing) housing systems as well as in coin cell architectures or in wounded configuration.

Flexible and highly stretchable nanostructured electrodes have been fabricated with a cost effective and scalable process by transferring Laser Induced Graphene (LIG) obtained on polyimide onto PDMS. Symmetric supercapacitors with good electrochemical storage performance, well maintained under mechanical bending and stretching, have been obtained employing a gel electrolyte based on PVP-1M NaCl.

Fig. 2 – a) Laser writing on polyimide for obtaining LIG (Laser Induced Graphene), b) LIG transfer onto PDMS, c) flexible and stretchable LIG-based electrodes, d) Cyclic voltammetry upon different bending conditions

Wire-shaped supercapacitors exploiting innovative synthesis approaches are under study for e-textile applications. Graphene aerogel self-assembly procedure on copper wire was obtained by easy hydrothermal reaction of GO dispersion. Precursor reduction and winding self-assembly around the copper wire take place during the process. Polymeric electrolyte-coated wires were used as symmetric electrodes into flexible wearable supercapacitors revealing superior energy storage behavior.

Fig. 3 – Wire-shapes EDLC supercapacitor, a) and b) FESEM images at different magnification of the Cu/rGO-aerogel interface

Micro supercapacitors exploiting the MEMS technology to embed a Graphene based material are studied following all the steps from the design, through the fabrication, to the final electrochemical tests. Interdigitated electrode patterns are designed for the increase of the exposed surface area in order to maximize the ionic interaction with the surface of the active material. The fabrication of the devices is conducted through the use of conventional semiconductor fabrication processes in a clean room environment. Besides more traditional Si based devices, polymer microsupercapacitors take advantages from replication techniques that are able to lower the costs of the single device and to exploit the flexibility of the substrate.

Fig. 4 – Flexible Micro-supercapacitors: (a) the interdigitated architecture in PDMS with graphene-based active material and graphite collectors, (b) the device dimensions, (c) the measurement in the characterization set-up

Contact information

Stefano Bianco
stefano.bianco@polito.it

Simone Marasso
simone.marasso@polito.it

Andrea Lamberti
andrea.lamberti@polito.it

Elena Tresso
elena.tresso@polito.it

Hybrid Devices for Energy Storage and Harvesting

Flexible and portable devices for energy harvesting and storage are fabricated by coupling DSSC and electrical double layer supercapacitors (EDLCs). Metal grids are employed for current collectors, and a methacrylate based quasi-solid polymer activated by soaking in two different liquids is used as electrolyte/separator. The device performance is tested under different illumination and bending conditions. An overall energy efficiency (conversion + storage) of 1.02% under STC (100 mW cm-1 and AM1.5G spectrum) has been demonstrated.

Fig. 1 – Integrated harvesting/storage energy devices: photo-charging (left) and discharging (center) processes, photo-charging curves obtained at 1 Sun under different bending conditions (right)

Contact information

Stefano Bianco
stefano.bianco@polito.it

Alberto Scalia
alberto.scalia@polito.it

Andrea Lamberti
andrea.lamberti@polito.it

Elena Tresso
elena.tresso@polito.it

Publications

1. G. Massaglia, M. Quaglio, “ The role of microfluidics and material selection for optimized energy conversion in Microbial Fuel Cells” book Chapter in "Green Chemistry - Bioelectrochemical Systems," Editor: R. Farooq,  IntechOpen Limited,  2018
2. G.P. Salvador, M. Gerosa, A. Sacco, N. Garino, M. Castellino, G. Massaglia, L. Delmondo, V. Agostino, V. Margaria, A. Chiodoni, M. Quaglio, Energy Technol. 2018, 6, 1– 9
3. G. Massaglia, M. Gerosa, V. Agostino, A. Cingolani, A. Sacco, G. Saracco, V. Margaria, M. Quaglio, Fuel Cells 2017, 17, 627–634
4. A. Sacco, N. Garino, A. Lamberti, C.F. Pirri, M. Quaglio, Appl. Surf. Sci, 2017,447-454
5. L. Delmondo,  J. A. Muñoz-Tabares, A. Sacco, N. Garino,  G. Massaglia,  M. Castellino,  G. P. Salvador,  C. F. Pirri,  M. Quaglio and  A. Chiodoni, Phys. Chem. Chem. Phys., 2017,19, 28781-28787
6. V. Agostino, D. Ahmed, A. Sacco, V. Margaria, C. Armato, M. Quaglio, Electrochimica Acta 2017, 237, 133-143
7. V. Margaria, T. Tommasi, S. Pentassuglia, V. Agostino, A. Sacco, C. Armato, A. Chiodoni, T. Schilirò, M. Quaglio, Int. J. Hydrog. Energy. 2017, 42, 3
8. N. Garino, A. Sacco, M. Castellino, J.A. Munoz-Tabares, A. Chiodoni, V. Agostino, V. Margaria, M. Gerosa, G. Massaglia, M. Quaglio, ACS Appl. Mater. Interfaces 2016, 8, 7
9. L. Delmondo, G.P. Salvador, J.A. Muñoz-Tabares, A. Sacco, N. Garino, M. Castellino, M. Gerosa, G. Massaglia, A. Chiodoni, M. Quaglio, Appl. Surf. Sci, 2016, 388.
10. T. Tommasi, G. Salvador, M. Quaglio, Scientific Reports, 2016, 6, 29091
11. "Interfacial Effects in Solid-Liquid Electrolytes for Improved Stability and Performance of Dye-Sensitized Solar Cells", Bella, F., Popovic, J., Lamberti, A., Tresso, E., Gerbaldi, C., Maier, J., (2017), ACS Applied Materials and Interfaces, 9 (43), pp. 37797-37803
12. "Comparative spectroscopic approach for the dye loading optimization of sheet-like ZnO photoanodes for dye-sensitized solar cells", Shahzad, N., Pugliese, D., Cauda, V., Shahzad, M.I., Shah, Z., Baig, M.A., Tresso, E., (2017) Journal of Photochemistry and Photobiology A: Chemistry, 337, pp. 192-197
13. "Real time monitoring of ultrafast sensitization for Dye-Sensitized Solar Cell photoanodes", Shahzad, N., Lamberti, A., Pugliese, D., Shahzad, M.I., Tresso, E., (2016) Solar Energy, 130, pp. 74-80
14. "Toward Totally Flexible Dye-Sensitized Solar Cells Based on Titanium Grids and Polymeric Electrolyte", Gerosa, M., Sacco, A., Scalia, A., Bella, F., Chiodoni, A., Quaglio, M., Tresso, E., Bianco, S., (2016) IEEE Journal of Photovoltaics, 6 (2), art. no. 7384432, pp. 498-505
15. "Floating, Flexible Polymeric Dye-Sensitized Solar-Cell Architecture: The Way of Near-Future Photovoltaics", Bella, F., Lamberti, A., Bianco, S., Tresso, E., Gerbaldi, C., Pirri, C.F., (2016) Advanced Materials Technologies, 1 (2), art. no. 1600002
16. "Dye-sensitized solar cell for a solar concentrator system", Sacco, A., Gerosa, M., Bianco, S., Mercatelli, L., Fontana, R., Pezzati, L., Quaglio, M., Pirri, C.F., Tucci, A.O.M., (2016) Solar Energy, 125, pp. 307-313
17. "All-SPEEK flexible supercapacitor exploiting Laser-induced graphenization", Lamberti, A., Serrapede, M., Ferraro, G., Fontana, M., Perrucci, F., Bianco, S., Chiolerio, A., Bocchini, S., (2017) 2D Materials, 4 (3), art. no. 035012
18. "Highly Uniform Anodically Deposited Film of MnO2 Nanoflakes on Carbon Fibers for Flexible and Wearable Fiber-Shaped Supercapacitors", Rafique, A., Massa, A., Fontana, M., Bianco, S., Chiodoni, A., Pirri, C.F., Hernández, S., Lamberti, A., (2017) ACS Applied Materials and Interfaces, 9 (34), pp. 28386-28393
19. "Flexible wire-based electrodes exploiting carbon/ZnO nanocomposite for wearable supercapacitors", Rafique, A., Bianco, S., Fontana, M., Pirri, C.F., Lamberti, A., (2017) Ionics, 23 (7), 1839
20. "Graphene/ruthenium active species aerogel as electrode for supercapacitor applications", Gigot, A., Fontana, M., Pirri, C.F., Rivolo, P., (2017) Materials, 11 (1), art. no. 57
21. "In situ MoS2 Decoration of Laser-Induced Graphene as Flexible Supercapacitor Electrodes", Clerici, F., Fontana, M., Bianco, S., Serrapede, M., Perrucci, F., Ferrero, S., Tresso, E., Lamberti, A., (2016) ACS Applied Materials and Interfaces, 8 (16), pp. 10459-10465
22. "Mixed 1T-2H Phase MoS2/Reduced Graphene Oxide as Active Electrode for Enhanced Supercapacitive Performance", Gigot, A., Fontana, M., Serrapede, M., Castellino, M., Bianco, S., Armandi, M., Bonelli, B., Pirri, C.F., Tresso, E., Rivolo, P., (2016) ACS Applied Materials and Interfaces, 8 (48), pp. 32842-32852
23. "Self-assembly of graphene aerogel on copper wire for wearable fiber-shaped supercapacitors", Lamberti, A., Gigot, A., Bianco, S., Fontana, M., Castellino, M., Tresso, E., Pirri, C.F., (2016) Carbon, 105, pp. 649-654
24. "Flexible solid-state CuxO-based pseudo-supercapacitor by thermal oxidation of copper foils", Lamberti, A., Fontana, M., Bianco, S., Tresso, E., (2016) International Journal of Hydrogen Energy, 41 (27), pp. 11700-11708
25. "A novel graphene based nanocomposite for application in 3D flexible micro- supercapacitors", S.L. Marasso, P. Rivolo, R. Giardi, D. Mombello, A. Gigot, M. Serrapede, S. Benetto, A. Enrico, M. Cocuzza, E. Tresso, C.F. Pirri, Materials Research Express, 2016, Vol. 3(6)
26. "A highly stretchable supercapacitor using laser-induced graphene electrodes onto elastomeric substrate", Lamberti, A., Clerici, F., Fontana, M., Scaltrito, L., (2016) Advanced Energy Materials, 6 (10), art. no. 1600050
27. "New insights on laser-induced graphene electrodes for flexible supercapacitors: Tunable morphology and physical properties", Lamberti, A., Perrucci, F., Caprioli, M., Serrapede, M., Fontana, M., Bianco, S., Ferrero, S., Tresso, E., (2017) Nanotechnology, 28 (17), art. no. 174002
28. "A flexible and portable powerpack by solid-state supercapacitor and dye-sensitized solar cell integration", Scalia, A., Bella, F., Lamberti, A., Bianco, S., Gerbaldi, C., Tresso, E., Pirri, C.F., (2017) Journal of Power Sources, 359, pp. 311-321
29. "High energy and high voltage integrated photo-electrochemical double layer capacitor", Scalia, A.; Varzi, A.; Lamberti, A; Tresso, E; Jeong, S. S.; Jacob, T.; Passerini, S., SUSTAINABLE ENERGY & FUELS. - 2(2018), pp. 968-977.
30. "A multipolymer electrolyte membrane designed by oxygen inhibited UV-crosslinking for integrated energy conversion and storage device", Scalia, A.; Lamberti, A.; Tresso, E.; Gerbaldi, C.; Bella, F.., Presentation at the 16th International Symposium on Polymer Electrolytes (ISPE-16) Yokohama (Japan) une 24-29, 2018.