TiO2 nanotubes layers as anodes for Li-ion micro batteries

Department of Flexible Electronics INSPIRING INNOVATION SINCE 1816 TiO2 nanotubes layers as anodes for Li-ion micro batteries Thierry Djenizian 9 October 2024 Department of Flexible Electronics 2 (R)Evolution of wearable technologies Department of Flexible Electronics 3 Microbatteries for wearable technologies Department of Flexible Electronics 4 The Li-ion technology Discharge Charge Reduction: A + Li+ + e- = Li+,AOxydation: C-,Li+ = C + Li+ + eOxydation: Li+,A- = A + Li+ + eReduction: C + Li+ + e- = C-,Li+ C + Li+,A- = A + C-,Li+ A + C-,Li+ = C + Li+,A- Department of Flexible Electronics 5 State of the arts Fabrication by thin-film techniques Department of Flexible Electronics 6 State of the arts Advantages of nano-architectured electrodes: nanowires, nanotubes, core-shell nanoparticles,... •Larger specific area for Li+accommodation •Support the volume changes during cycling •Short diffusion length •Appropriate to flexible systems ! Department of Flexible Electronics 7 Electrolyte: LiPF6 (EC:EDC) TiO2+ xLi++ xe-↔ LixTiO2 Ortiz et al, Chem. Mater., 21, 63, 2009 Ortiz et al, Electrochim. Acta, 554, 4262, 2009 Ortiz et al, Chem. Mater., 22, 1926, 2010 Djenizian et al, J. Mat. Chem., 21, 9925, 2011 (review) No binder and no additive Titania nanotubes as anode for Li-ion batteries Ti+2H2O→TiO2+4H++4e− TiO2+6F−+4H+→TiF 6 2−+2H2O Department of Flexible Electronics 8 Fabrication of solid-state Li-ion microbatteries SEM images of cross section of the all-solid-state battery composed of TiO2nts/MA-PEG300/LNMO N. Plylahan, M. Letiche, M. Barr, T. Djenizian, Electrochem. Commun.,43, 121, 2014 020 40 60 80 100 0 40 80 120 160 200 0 15 30 46 61 76 * Gravimetric*capaicty*(mAh*g:1) *Areal*capacity*(µAh*cm:2*µm:1)* * * Cycle*number ! Discharge capacity versus anode at multi C-rate Department of Flexible Electronics 9 ! !"#! !$#! !%#!!&#! ! !"#! !$#! !%#! !&#! SEM confirms the electrodeposition of polymer N. Plylahan, S. Maria, T. N. T. Phan, M. Letiche, H. Martinez, C. Courreges, P. Knauth, and T. Djenizian, Nanoscale Res. Lett., 9, 544 (2014) N. Plylahan, N. A. Kyeremateng, M. Eyraud, F. Dumur, H. Martinez, L. Santinacci, P. Knauth, T. Djenizian, Nanoscale Res. Lett., 7, 349 (2012) Conformal electrodeposition of polymer electrolyte Electrolyte: 0.5M LiTFSI + 0.5M MA-(PEO)5 Department of Flexible Electronics 16 Influence of the TiO2 nanotube thickness C. Ghigo, H. Sopha, M. Sepúlveda, L. Hromadko, J. Rodriguez-Pereira, F. Vacandio, K. Denoue, J. Macak, T. Djenizian, Energy Technology, 2024, in press. Department of Flexible Electronics 17 Anodization of alloy based Ti substrates Self-supported Niobium-doped TiO2nanotubes as a negative electrode G. D. Salian, B. M. Koo, C. Lefevre, T. Cottineau, C. Lebouin, A. T. Tesfaye, P. Knauth, V. Keller, T. Djenizian Adv. Mater. Technol., 3, 1700274 (2017) Department of Flexible Electronics 18 ALD Al2O3-coated TiO2nanotube layers as anode H. Sopha, G. D. Salian, R. Zazpe, J. Prikryl, L. Hromadko, T. Djenizian, J. M. Macak, ACS Omega, 2, 2749 (2017) ALD coatings Department of Flexible Electronics 19 ALD growth of MoS2nanosheets on TiO2nanotubes H. Sopha, A. T. Tesfaye, R. Zazpe, J. Michalika, F. Dvorak, L. Hromadko, M. Krbal, J. Prikryl, T. Djenizian, J. M. Macak, FlatChem,17, 100130 (2019) ALD coatings Department of Flexible Electronics 20 TiO2nanotubes decorated with Al203/MoS2/Al203 A. T. Tesfaye, H. Sopha, A. Ayobi, R. Zazpe, J. Rodriguez-Pereira, J. Michalika, S. Ng, Z. Spotz, L. Hromadko, J. Prikryl, J. M. Macak, T. Djenizian, Nanomaterials, 10, 953 (2020) ALD coatings Department of Flexible Electronics 21 Chemical modification of nanotubes Decoration of nanotubes with TiO2 NPs H. Sopha, C. Ghico, S. Ng, M. Alijani, L. Hromadko, J. Michalicka, T. Djenizian, J. Macak,Materials Chemistry and Physics,276,125307 (2022) SEM images of the a) blank TNT layer, and TNT layers decorated with b) 1 dip TiO2NPs, c) 2 dips TiO2NPs, d) 3 dips TiO2NPs, e) 4 dips TiO2NPs, and f) 7 dips TiO2NPs. Department of Flexible Electronics 22 Sulphurized TiO2nanotubes as cathode for lithium-ion batteries TEM-EDS image G. D. Salian, M. Krbal, H. Sopha, C. Lebouin, M. V. Coulet, J. Michalika, L. Hromadko, A. T. Tesfaye, J. M. Macak, T. Djenizian, Applied Materials Today, 16, 257 (2019) Chemical modification of nanotubes Department of Flexible Electronics 23 To summarize… Department of Flexible Electronics 24 Influence of the geometry substrate V. A. Sugiawati, F. Vacandio, A. Galeyeva, A. P. Kurbatov, T. Djenizian, Frontiers in Physics, 7, 179 (2019) Department of Flexible Electronics 25 Porous oxide nanolaminates as anode materials Mn+1AXnare 3D layered ternary carbides or nitrides M: early transition metal (Ti, Nb, Mo, V, etc.) A: IIIA and IVA group elements (Al, Si, Ge, etc.) X: C and/or N Selective etching of Ti3SiC2 or Ti2SC by anodization in HF-containing electrolyte •M. Q. Zhao, M. Sedran, Z. Ling, M. Lutkatskaya, O. Mashtalir, M. Ghidiu, B. Dyatkin, D. J. Tallman, and T. Djenizian, M. W. Barsoum, and Y. Gogotsi, Angew. Chem. Int. Ed. Eng., 54, 4810 (2015). VIP Paper •A. T. Tesfaye, O. Mashalir, M. Naguib, M. W. Barsoum, Y. Gogotsi and T. Djenizian, ACS Appl. Mater. Interfaces, 7, 20495 (2016) •A. T. Tesfaye, Y. Gogotsi and T. Djenizian, Electrochem. Commun., in press (2017) Anodization of MAX phases Department of Flexible Electronics • Bioresorbable TMIs need new transient energy systems ØRechargeable battery technologies including Li-ion batteries are using toxic elements that cannot be safely degraded by the body and must be then removed by surgery and recycled after use •A rechargeable wearable power source in which all constituents are non-toxic and able to be degraded by physiological fluids have not been achieved yet ØPropose a new technology able to penetrate the biomedical market and revolutionize the bioresorbable electronics The main challenges Our successful achievement: Design a high performance battery that is implantable, bioresorbable, wireless rechargeable with a controlled lifetime (from days to several months) A Na-ion bioresorbable and flexible electrochemical accumulator. Patent # EP23170468.5, 2023 Bioresorbable battery Department of Flexible Electronics Wireless charging of implanted battery The main concept Bioresorbable battery Department of Flexible Electronics The fabrication process Bioresorbable battery A Na-ion bioeliminable electrochemical accumulator comprising electrode pellets coated by a current collector thin film, Associated manufacturing process and wireless recharging solution. Patent #EP24306269.2., 2024 Bioresorbable and Wireless Rechargeable Implanted Na-ion Battery for Temporary Medical Devices, under revision Department of Flexible Electronics Current collectors: Mg Anode: NTPC, carbon black, sodium alginate Cathode: NMO, carbon black, sodium alginate Polymer electrolyte: Sodium sulfate, sodium alginate Bioresorbable battery Bioresorbable and Wireless Rechargeable Implanted Na-ion Battery for Temporary Medical Devices, under revision Department of Flexible Electronics Electrochemical characterization and KPIs Main features Diameter 0.74 cm Thickness 0.12 cm Surface 0.43 cm2 Volume 0.05 cm3 Mass 90 mg Bio-elimination time One day –several months Key Performance Indicators @C/2rate 1st discharge capacity 1.2 mAh Capacity retention 83 % after 50 cycles Energy 0.78 mWh Power 1.17 mW Wireless recharging characteristics Recharge at 4 mm 30 min Recharge at 12 mm 1 h Bioresorbable battery Bioresorbable and Wireless Rechargeable Implanted Na-ion Battery for Temporary Medical Devices, under revision Department of Flexible Electronics In vitro & in vivo studies üBio-elimination üToxicity Bioresorbable battery Bioresorbable and Wireless Rechargeable Implanted Na-ion Battery for Temporary Medical Devices, under revision Department of Flexible Electronics üElimination time is controlled by the PLGA thickness üDesign of “on-demand” bioresorbable batteries that may operate days or several weeks ✕The matter of carbon black… See the UNIMORE presentation Bioresorbable battery In vitro & in vivo studies Bioresorbable and Wireless Rechargeable Implanted Na-ion Battery for Temporary Medical Devices, under revision Department of Flexible Electronics Bioresorbable battery Bioresorbable and Wireless Rechargeable Implanted Na-ion Battery for Temporary Medical Devices, under revision Department of Flexible Electronics Wireless recharging Bioresorbable battery Bioresorbable and Wireless Rechargeable Implanted Na-ion Battery for Temporary Medical Devices, under revision Department of Flexible Electronics ØImprove the battery performance ØDesign of a bioresorbable charging layer ØIntegration of different building blocks developed in RESORB for the proof-of-concept Bioresorbable battery