Fabrication and modification of TiO2 nanotubes for high- performance Li-ion micro batteries

Department of Flexible Electronics INSPIRING INNOVATION SINCE 1816 Fabrication and modification of TiO2 nanotubes for highperformance Li-ion micro batteries Thierry Djenizian 8 July 2024 Department of Flexible Electronics 2 4 •Flexible Electronics •Bioelectronics •Systems and secured architectures •Fabrication Sciences & Logistics Research departments 120 Staff 26 7 Researchers Eng. & technicians 2,5 M€ + Research projects 60+ Peer-reviewed scientific articles/y 3 Technological platforms •Clean room (600 m2) •ID-FAB for prototyping •MicroPacks 5 82 Administrative PhD students & post-doc Department of Flexible Electronics 3 3 technological platforms •Clean room facili-es •MicroPacks (20 companies) • ID Fab (prototyping) Department of Flexible Electronics 4 Flexible Electronics Department 8 Professors-researchers 10 PhD 1 Research Ing. 6 Postdoctol fellows Department of Flexible Electronics 5 The research context Applications : IoT, wearables, medical devices,… passive components microcontroller memory sensor flexible substrate remote powering Department of Flexible Electronics 6 Competences and expertises Integration Devices Fabrication/printing of inks with advanced properties Synthesis of nanomaterials Sensors Antennas Storage of energy Transistors Materials Microstructuring of materials Department of Flexible Electronics 7 (R)Evolution of wearable technologies Department of Flexible Electronics 8 Microbatteries for wearable technologies Department of Flexible Electronics 9 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 16 Anodization of alloy based Ti substrates Self-supported Niobium-doped TiO2nanotubes as a negative electrode for lithium-ion microbatteries 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 17 ALD Al2O3-coated TiO2nanotube layers as anodes for lithium ion batteries 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 18 ALD coatings 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) Department of Flexible Electronics 19 ALD coatings 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) Department of Flexible Electronics 20 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 21 Chemical modification of nanotubes 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) Department of Flexible Electronics 22 To summarize… Challenge : achieve the fabrication of thin-film microbatteries Department of Flexible Electronics 23 Fabrication of solid-state Li-ion microbatteries SEM images of cross section of the all-solid-state battery composed of TiO2nts/MA-PEG300/LNMO (a).Enlarged view of the self-organized TiO2nt (b) 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 24 ! !"#! !$#! !%#!!&#! ! !"#! !$#! !%#! !&#! 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 25 As-formed 5 cycles 10 cycles 25 cycles 50 cycles 100 cycles SEM images of the TiO2nanotubes aAer different cycles SEM analysis Department of Flexible Electronics 32 Porous oxide nanolaminates from MAX phases 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 SelecUve etching of Ti3SiC2 or Ti2SC by anodizaUon 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) Department of Flexible Electronics 33 Microbatteries for wearable technologies Department of Flexible Electronics 34 Number of scienAfic arAcles for flexible and stretchable baEeries in the last 20 years State-of-the-arts Department of Flexible Electronics 35 W. Weng, et al, Adv. Mater. 2015, 27, 1363 Q.-C. Liu, et al, Nat. Commun. 2015, 6, 7892 H. Li, Y. Ding, et al, Adv. Mater. 2017, 29, 1700898 H. Lin, et al, Adv. Mater. 2014, 26, 1217 Xu, et al, Nat. Commun. 2013 ,4, 1543 State-of-the-arts Department of Flexible Electronics 36 New concepts and designs Microbatteries Na-ion bio-eliminable battery Department of Flexible Electronics 37 Micropillar electrodes supported on serpentine current collectors by laser patterning Improvement of the electrode/electrolyte interfaces by using 3D materials for high capacity values (>> 1 mA h cm-2) R. Delattre, Th. Djenizian, "Deformable accumulator", WO/2018/167393 The stretchable battery Department of Flexible Electronics 38 The stretchable battery Stretched Bent Department of Flexible Electronics 39 The stretchable battery Department of Flexible Electronics 40 The stretchable battery Nasreldin, M.; Delattre, R.; Marchiori, B.; Ramuz, M.; Maria, S.; de Bougrenet de la Tocnaye, J.L.; Djenizian, T. Microstructured electrodes supported on serpentine interconnects for stretchable electronics., APL Mater. 7, 031507 (2019) Department of Flexible Electronics 41 The stretchable battery Department of Flexible Electronics 48 Objectives Department of Flexible Electronics 49 The stretchable battery 8 min 18 min 150 min Department of Flexible Electronics 50 The wire baEery Design a “Wire-shaped Flexible Microbattery” to power E-textile based wearable devices Wrist or chest band Smart socks Body suit Department of Flexible Electronics 51 The wire baEery T. Djenizian, V.K.A. Muniraj,R.Delattre, M. Ramuz, A metal-ion electrochemical accumulator, with electrodes with electrically conductive substrates forming the collectors which are wound in ahelix around each other, separated by aseparator also wound in ahelix and encapsulated in asheath.Application number:EP23167208.0., 2023-01 Department of Flexible Electronics 52 The wire battery Department of Flexible Electronics 53 The wire battery Cathode/Anode Voltage window Specific capacity at 0.1C rate Energy density LCO/LTO 1.5 –2.8 V 136 µAh cm " 129.5 Wh L " 1 LNMO/LTO 2.0 – 3.4 V 51 µAh cm " 121.7 Wh L " 1 NCA/LTO 1.0 – 3.4 V 55 µAh cm " 111 Wh L " 1 LCO/Graphite 3.0 – 4.2 V 40 µAh cm " 111.2 Wh L " 1 Department of Flexible Electronics 54 The wire baEery Department of Flexible Electronics (For temporary medical implants) •Provide a targeted and personlized therapy during a determined clinical time •Therapy: localized drug release, electrode stimulation, biosensing, communication,… •The ideal TMI should be entirely bioeliminable to avoid a second surgery or potential rejection Interest in temporary medical implants Example of a bioresorbable pacemaker for temporary heart stimulation Drawback: continously powered by external chargers DBS for stroke recovery and nerve regeneraUon by electrode sUmulaUon Drawback: powered by implanted permanent baVeries Bioeliminable rechargeable ba/ery 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, bioeliminable, flexible, wireless rechargeable with a controlled lifetime (from days to several months) (For temporary medical implants) A Na-ion bioresorbable and flexible electrochemical accumulator. Patent # EP23170468.5, 2023 Bioeliminable rechargeable ba/ery Department of Flexible Electronics Wireless charging of implanted baEery The main concept Bioeliminable rechargeable battery (For temporary medical implants)