GIOVANNA MARESCA

PhD Graduate

PhD program:: XXXVI


supervisor: Maria Assunta Navarra
co-supervisor: Giovanni Battista Appetecchi

Thesis title: COMPATIBILITY OF IONIC LIQUID ELECTROLYTES TOWARDS LI-ION AND NA-ION ELECTRODES

One of the major challenges of LIBs and SIBs is related to safety and reliability, which are mostly connected to the nature of the electrolyte. Commercial organic electrolytes show several critical issues, therefore different alternatives have been considered, such as polymers, ceramics, and ionic liquids. The experimental activities of the present PhD thesis have been structured in five sections: the first one was focused on synthesis, characterization, and selection of IL electrolytes. The other sections were addressed to investigation of compatibility and behaviour of the selected IL electrolytes with LIB (2nd and 3rdsections) and SIB (4th and 5thsections) systems, respectively. During the first section, different IL families were studied: in particular, imidazolium, tetra-alkyl-ammonium, and piperidinium cations, coupled with bis(perfluroalkylsulfonyl)imide anions, were considered as innovative safety electrolyte components for being addressed to LIB and SIB systems. The synthesis purification route is reported in detail and the quality level of the synthetized ILs was validated through X-Ray fluorescence analysis, UV-Vis spectrophotometry and Karl-Fisher titration. The thermal stability of the pure ILs was analyzed by thermogravimetric analysis (TGA) under helium atmosphere, through both temperature heating scan and isothermal steps. Li+ and Na+-conducting electrolyte formulations, based on 1-ethyl-3-methyl-imidazolium (EMI), trimethyl-butyl-ammonium (N1114), and N-alkyl-N-methyl-piperidinium (PIPn1) ionic liquid (IL) families were designed and investigated. Lithium bis(trifluoromethylsulfonyl)imide, LiTFSI, and sodium bis(trifluoromethylsulfonyl)imide, NaTFSI, were selected as the salts. The ion transport properties and electrochemical stability have been investigated, analyzing the dependence from the nature of the anion and the cation aliphatic side chain length. In the second section, LIB silicon nanowire anodes were investigated in lithium metal cells using electrolyte formulations (selected in the frame of the 1st section) based on EMITFSI, EMIFSI and N1114FSI ionic liquids. The lithium insertion process in the silicon anode was analyzed by cyclic voltammetry measurements, performed at different scan rates and for prolonged CV tests, combined with impedance spectroscopy analysis. The electrochemical performances were investigated by galvanostatic charge-discharge cycling tests. X-ray photoelectron spectroscopy (XPS) measurements were carried out onto the silicon nanowire electrode surface to gain knowledge about the SEI (Solid Electrochemical Interface) layer. In the third section, LIB cobalt-free, lithium-rich, layered oxide Li1.2Ni0.2Mn0.6O2 (LRLO) cathodes were investigated in the selected IL electrolytes. The battery performances, after previous screening of the IL formulations, were evaluated by prolonged galvanostatic charge-discharge cycling in Li/LRLO cells. The effect of the lithium salt was also assessed. The electrochemical process of Li+-insertion was analyzed through cyclic voltammetry measurements at increasing scan rates and for prolonged cycles. In the fourth section, SIB hard carbon (HC) anodes, obtained from natural biowaste, have been investigated in EMIFSI and N1114FSI electrolytes. The Na+ intercalation process was analyzed by cyclic voltammetry tests, performed at different scan rates for hundreds of cycles, in combination with impedance spectroscopy measurements to decouple bulk and interfacial resistances of the cells. Also, the Na+ diffusion coefficient in the HC host was determined via the Randles-Sevcik equation. The cell performance was evaluated by room temperature galvanostatic charge/discharge cycling tests. The evolution of the SEI (solid electrochemical interface) layer grown on the HC surface, cycled in different electrolytes, has been studied by Raman spectroscopy, XPS and focused ion beam milling scanning electron microscopy (FIB-SEM) analysis. In the last section, SIB monocline sodium manganite, α-NaMnO2, cathodes were investigated in EMIFSI and N1114FSI electrolytes. The Na+ insertion process in α-NaMnO2 was analyzed through cyclic voltammetry tests, carried out at different scan rates, combined with impedance spectroscopy measurements. The cell performance of α-NaMnO2 electrodes was validated by galvanostatic charge-discharge cycling tests whereas the surface composition and the morphology of post-mortem cathodes were analyzed through XPS and FIB-SEM measurements. My PhD research activities were carried out in the frame of two Projects: i) Si-DRIVE (Silicon Alloying Anodes for High Energy Density Batteries comprising Lithium Rich Cathodes and Safe Ionic Liquid based Electrolytes for Enhanced High VoltagE Performance), H2020-NMBP-ST-IND-2018” (Topic LC-NMBP-30-2018) Grant Agreement 814464, founded by the European Union’s Horizon 2020; ii) National Program (Electric Research System) Agreement (Energy storage systems for electrical network, Activity LA1.7: Ionic liquid electrolytes for sodium batteries) between the Italian Ministry of Ecological Transition and ENEA.

Research products

11573/1703901 - 2024 - Improved compatibility of α-NaMnO2 cathodes in ionic liquid electrolytes
Maresca, G.; Ottaviani, M.; Ryan, K. M.; Brutti, S.; Appetecchi, G. B. - 04d Abstract in atti di convegno
conference: 3rd Italian Workshop on Energy Storage (IWES 2024) (Rome (Italy))
book: 3rd Italian Workshop on Energy Storage (IWES 2024) - ()

11573/1719711 - 2024 - Physicochemical investigation on the hard carbon interface in ionic liquid electrolyte
Maresca, G.; Ottaviani, M.; Ryan, K. M.; Brutti, S.; Appetecchi, G. B. - 01a Articolo in rivista
paper: ELECTROCHIMICA ACTA (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. 1-8 - issn: 0013-4686 - wos: (0) - scopus: 2-s2.0-85198002688 (0)

11573/1704875 - 2024 - Superior compatibility of silicon nanowire anodes in ionic liquid electrolytes
Maresca, Giovanna; Sankaran, Abinaya; Santa Maria, Luigi J.; Ottaviani, Michela; Fantini, Sebastien; Ryan, Kevin M.; Brutti, Sergio; B. Appetecchi., Giovanni - 01a Articolo in rivista
paper: ENERGY MATERIALS (Alhambra California: OAE Publishing Inc., 2021-) pp. 1-19 - issn: 2770-5900 - wos: WOS:001272074700006 (4) - scopus: (0)

11573/1668669 - 2023 - Effects of difluoro(oxalato)borate-based ionic liquid as electrolyte additive for Li-ion batteries
Di Donato, Graziano; Maresca, Giovanna; Palluzzi, Matteo; Tsurumaki, Akiko; Navarra, Maria Assunta - 01a Articolo in rivista
paper: MATERIALS (Basel: Molecular Diversity Preservation International-MDPI) pp. 1411- - issn: 1996-1944 - wos: WOS:000941566800001 (2) - scopus: 2-s2.0-85149254765 (3)

11573/1663517 - 2023 - An electrochemical compatibility investigation of {RTIL}-based electrolytes with Si-based anodes for advanced Li-ion batteries
Falco, Marisa; Lingua, Gabriele; Destro, Matteo; Silvestri, Laura; Meligrana, Giuseppina; Lin, Rongying; Fantini, S('(E))Bastien; Maresca, Giovanna; Paolone, Annalisa; Brutti, Sergio; Appetecchi, Giovanni B.; Elia, Giuseppe Antonio; Gerbaldi, Claudio - 01a Articolo in rivista
paper: MATERIALS TODAY SUSTAINABILITY (Kidlington: Elsevier Ltd.) pp. 100299- - issn: 2589-2347 - wos: WOS:000925497600001 (3) - scopus: 2-s2.0-85146586383 (3)

11573/1703894 - 2023 - Ionic liquid electrolytes for sodium battery systems
Maresca, G.; Brutti, S.; Appetecchi, G. B. - 04d Abstract in atti di convegno
conference: 2nd Italian Workshop on Energy Storage (IWES 2023) (Bressanone (TN), Italy)
book: 2nd Italian Workshop on Energy Storage (IWES 2023) - ()

11573/1703890 - 2023 - Compatibility of ionic liquid electrolytes towards large-capacity, nanowire, silicon anodes and high-voltage, lithium-rich, nickel-manganese oxide cathodes.
Maresca, G.; Di Schiavi, A.; Brutti, S.; Paolone, A.; Palumbo, O.; Fantini, S.; Lin, R.; Martin, P. A.; Choi, H.; Kuenzel, M.; Passerini, S.; Sankaran, A.; Geaney, H.; Ryan, K. M.; Appetecchi, G. B. - 04d Abstract in atti di convegno
conference: Actea 2023 (Frascati, Italy)
book: Actea2023 - ()

11573/1703895 - 2023 - Ionic Liquid Electrolytes for Sodium-Ion Battery Systems
Maresca, G.; Petrongari, A.; Brutti, S.; Appetecchi, G. B. - 04d Abstract in atti di convegno
conference: Giornate dell’Elettrochimica Italiana (GEI) 2023 (Cefalù (Italy))
book: Giornate dell’Elettrochimica Italiana (GEI) 2023 - ()

11573/1686589 - 2023 - Outstanding compatibility of hard-carbon anodes for sodium-ion batteries in ionic liquid electrolytes
Maresca, Giovanna; Petrongari, Angelica; Brutti, Sergio; Appetecchi, Giovanni Battista - 01a Articolo in rivista
paper: CHEMSUSCHEM (WEINHEIM, GERMANY: WILEY-V C H VERLAG GMBH) pp. - - issn: 1864-5631 - wos: WOS:001059815500001 (2) - scopus: 2-s2.0-85170039444 (3)

11573/1663516 - 2022 - Silicon-based composite anodes for all-solid-state lithium-ion batteries conceived by a mixture design approach
Branchi, Mario; Maresca, Giovanna; Tsurumaki, Akiko; Suzuki, Naoki; Croce, Fausto; Panero, Stefania; Voje, Jorunn; Aihara, Yuichi; Navarra, Maria Assunta - 01a Articolo in rivista
paper: CHEMSUSCHEM (WEINHEIM, GERMANY: WILEY-V C H VERLAG GMBH) pp. 1-8 - issn: 1864-5631 - wos: WOS:000928818200001 (2) - scopus: 2-s2.0-85147265929 (5)

11573/1629848 - 2022 - Sodium-conducting ionic liquid electrolytes: electrochemical stability investigation
Maresca, Giovanna; Casu, Paolo; Simonetti, Elisabetta; Brutti, Sergio; Battista Appetecchi, Giovanni - 01a Articolo in rivista
paper: APPLIED SCIENCES (Basel: MDPI AG, 2011-) pp. 4174- - issn: 2076-3417 - wos: WOS:000795281700001 (7) - scopus: 2-s2.0-85129203377 (8)

11573/1663515 - 2022 - Synthesis, physical properties and electrochemical applications of two ionic liquids containing the asymmetric (fluoromethylsulfonyl)(trifluoromethylsulfonyl)imide anion
Palumbo, Oriele; Appetecchi, Giovanni Battista; Maresca, Giovanna; Brubach, Jean-Blaise; Roy, Pascale; Di Muzio, Simone; Trequattrini, Francesco; Bordignon, Delphine; Legrand, Florine; Falgayrat, Anaãs; Lin, Rongying; Fantini, Sebastien; Paolone, Annalisa - 01a Articolo in rivista
paper: APPLIED SCIENCES (Basel: MDPI AG, 2011-) pp. 4524- - issn: 2076-3417 - wos: WOS:000794670600001 (3) - scopus: 2-s2.0-85129726726 (3)

11573/1627444 - 2022 - So similar, yet so different: the case of the ionic liquids N-trimethyl-N(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide and N,N-diethyl-N-methyl-N(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide
Palumbo, Oriele; Sarra, Angelo; Brubach, Jean-Blaise; Trequattrini, Francesco; Cimini, Adriano; Brutti, Sergio; Battista Appetecchi, Giovanni; Simonetti, Elisabetta; Maresca, Giovanna; Fantini, Sébastien; Lin, Rongying; Falgayrat, Anaïs; Roy, Pascale; Paolone, Annalisa - 01a Articolo in rivista
paper: FRONTIERS IN PHYSICS (Lausanne : Frontiers Editorial Office, 2013-) pp. - - issn: 2296-424X - wos: WOS:000779004600001 (3) - scopus: 2-s2.0-85127947681 (2)

11573/1703893 - 2021 - Sodium-conducting, ionic liquid electrolytes for Na battery systems
Maresca, G.; Casu, P.; Bellusci, M.; Simonetti, E.; Brutti, S.; Appetecchi, G. B. - 04d Abstract in atti di convegno
conference: SCI 2021 - XXVII Congresso Nazionale della Società Chimica Italiana (online)
book: SCI 2021 - XXVII Congresso Nazionale della Società Chimica Italiana - ()

11573/1703891 - 2021 - Compatibility of ionic liquid electrolytes towards large-capacity, nanowire, silicon anodes and high-voltage, lithium-rich, nickel-manganese oxide cathodes
Maresca, G.; Di Schiavi, A.; Simonetti, E.; Brutti, S.; Paolone, A.; Palumbo, O.; Fantini, S.; Lin, R.; Martin, P. I.; Falgayrat, A.; Choi, H.; Kuenzel, M.; Passerini, S.; Sankaran, A.; Geaney, H.; Ryan, K. M.; Appetecch, G. B. - 04d Abstract in atti di convegno
conference: E-MRS 2021 (European Material Research Society) (Online)
book: E-MRS 2021 (European Material Research Society) - ()

11573/1575681 - 2021 - Sn/C composite anodes for bulk-type all-solid-state batteries
Maresca, G.; Tsurumaki, A.; Suzuki, N.; Yoshida, K.; Panero, S.; Aihara, Y.; Navarra, M. A. - 01a Articolo in rivista
paper: ELECTROCHIMICA ACTA (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. 139104- - issn: 0013-4686 - wos: WOS:000697727000003 (9) - scopus: 2-s2.0-85114836222 (11)

11573/1464484 - 2021 - Improvement of graphite interfacial stability in all-solid-state cells adopting sulphide glassy electrolytes
Maresca, Giovanna; Tsurumaki, Akiko; Suzuki, Naoki; Tsujimura, Tomoyuki; Aihara, Yuichi; Navarra, Maria Assunta - 01a Articolo in rivista
paper: CHEMELECTROCHEM (Weinheim: Wiley-VCH) pp. 689-696 - issn: 2196-0216 - wos: WOS:000608280200001 (11) - scopus: 2-s2.0-85100016305 (11)

11573/1270067 - 2019 - Ionic liquid electrolytes for room temperature sodium battery systems
Brutti, S.; Navarra, M. A.; Maresca, G.; Panero, S.; Manzi, J.; Simonetti, E.; Appetecchi, G. B. - 01a Articolo in rivista
paper: ELECTROCHIMICA ACTA (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. 317-326 - issn: 0013-4686 - wos: WOS:000464148700034 (27) - scopus: 2-s2.0-85063622773 (30)

11573/1251413 - 2017 - Highly conductive, ionic liquid-based polymer electrolytes
Simonetti, E.; Carewska, M.; Maresca, G.; De Francesco, M.; Appetecchi, G. B. - 01a Articolo in rivista
paper: JOURNAL OF THE ELECTROCHEMICAL SOCIETY (Electrochemical Society:65 South Main Street, Building D:Pennington, NJ 08534:(609)737-1902, EMAIL: ecs@electrochem.org, orders@electrochem.org, INTERNET: http://www.electrochem.org, Fax: (609)737-2743) pp. A6213-A6219 - issn: 0013-4651 - wos: WOS:000394508400035 (37) - scopus: 2-s2.0-85012902914 (37)

11573/1251415 - 2016 - Towards Li(Ni0.33 Mn0.33 Co0.33 )O2 /graphite batteries with ionic liquid-based electrolytes. I. Electrodes' behavior in lithium half-cells
Simonetti, E.; Maresca, G.; Appetecchi, G. B.; Kim, G. -T.; Loeffler, N.; Passerini, S. - 01a Articolo in rivista
paper: JOURNAL OF POWER SOURCES (Elsevier BV:PO Box 211, 1000 AE Amsterdam Netherlands:011 31 20 4853757, 011 31 20 4853642, 011 31 20 4853641, EMAIL: nlinfo-f@elsevier.nl, INTERNET: http://www.elsevier.nl, Fax: 011 31 20 4853598) pp. 426-434 - issn: 0378-7753 - wos: WOS:000385601200047 (23) - scopus: 2-s2.0-84991051850 (26)

11573/1251417 - 2014 - Mixed organic compound-ionic liquid electrolytes for lithium battery electrolyte systems
Montanino, M.; Moreno, M.; Carewska, M.; Maresca, G.; Simonetti, E.; Lo Presti, R.; Alessandrini, F.; Appetecchi, G. B. - 01a Articolo in rivista
paper: JOURNAL OF POWER SOURCES (Elsevier BV:PO Box 211, 1000 AE Amsterdam Netherlands:011 31 20 4853757, 011 31 20 4853642, 011 31 20 4853641, EMAIL: nlinfo-f@elsevier.nl, INTERNET: http://www.elsevier.nl, Fax: 011 31 20 4853598) pp. 608-615 - issn: 0378-7753 - wos: WOS:000340975200074 (61) - scopus: 2-s2.0-84905041597 (63)

11573/556599 - 2014 - Sodium-conducting ionic liquid-based electrolytes
Serra Moreno, Judit; Maresca, G.; Panero, Stefania; Scrosati, Bruno; Appetecchi, Giovanni Battista - 01a Articolo in rivista
paper: ELECTROCHEMISTRY COMMUNICATIONS (Tokyo ; Oxford ; New York ; Amsterdam ; Lausanne ; Shannon : Elsevier) pp. 1-4 - issn: 1388-2481 - wos: WOS:000337555700001 (53) - scopus: 2-s2.0-84896508886 (55)

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