Societal, Scientific, and Technological Context
Mankind is facing in the 21st century a rapidly increasing demand for efficient energy generation and storage solutions to fulfill a societal basic need crystallized in the United Nation Sustainable Development Goal (SDG) N°7 : Ensure access to affordable, reliable, sustainable and modern energy for all. These pressing demands are calling for innovation breakthroughs unlocking future (already foreseen) technological roadblocks for a safer/cleaner (decarbonized) energy generation (i.e. optimizing the right energy mix) balanced by the equally important access to energy storage 2.0 solutions to ensure a doable energetic balance on a planet with finite resources. These acute and critical issues create unprecedented challenging but truly stimulating opportunities for researchers to produce sizeable and transformative impacts to benefiting our societies. This is particularly true for developing future electrochemical energy storage solutions, which depend on the advancement of science and technology to allow for safer by design rechargeable batteries with enhanced energy densities.
Within this context, the development of next generation reactive metal (e.g. Li, Na or K) anode-based batteries is foreseen as promising key-enabling technologies. For rechargeable Lithium-Based Batteries (LiBs), the metallic anode would indeed allow for a tenfold increase in specific capacity compared to a graphite anode. Nevertheless, the commercialization of secondary Lithium Metal Batteries (LMBs) will only become feasible when current safety and performance problems will have been overcome: i) Leakage, poor chemical stability, flammability, and parasitic reactions with Li metal, ii) unstable and dendritic lithium deposition, and iii) rather limited performances of organic (liquid) electrolytes. These issues are in part associated with the heart of LiBs, i.e. the electrolytes: Liquid organic electrolytes with low cationic transference numbers, and relatively low ionic conductivities and poor mechanical properties for salt-in-polymer (Solid) Polymer Electrolytes (SPEs). This is calling for a new blueprint to trigger innovation breakthroughs allowing long lasting and efficient cell chemistries unlocking the commercialization path to (very much) awaited safer by design and higher performances secondary batteries.
Objectives & Rational
In line with the trajectory of the ten-year long Battery 2030+ European initiative (Website: https://battery2030.eu/ : Manifesto & Roadmap), this PhD project aims at developing a new blue print for self-healing LMBs. To realize this ambition and go beyond the State-of-the-Art (SoA), this basic research-oriented project is grounded onto a functional soft-matter-based class of organic electrolytes 2.0: Thermotropic Ionic Liquid Crystals (TILCs). These tunable-by-design ionically conducting (Li+ Na+ , K+ ) electrolytes represent the fusion of two known class of materials: the stimuli-responsive & dynamically self-assembling Thermotropic Liquid Crystals (TLCs) and cationic (Li+ /Na+ /K+ ) organic conductors. Its overarching goal and rational will be to deliver proof of concept demonstrations of their self-healing ability combined with efficient nanoconfined cationic transport functionality within prescribed 1D, 2D or 3D morphologies connecting the Li Metal anode and the cathode of LMBs.
PhD Research Tasks
The PhD candidate will be in charge of designing, synthesizing, and characterizing (the structure & dynamics) of TILCs. She/He will address two fundamental questions for advanced nanostructured organic electrolytes: i) the role of (1D vs. 2D vs. 3D) dimensionality onto the percolation and nanoconfinement of charge carriers within multiscale phase-segregated electrolyte with hierarchically self-organized insulating & conducting sub-phases & ii) the dynamic mosaicity & the defect management in functional soft matter, with or without external stimuli.
She/He will be also in charge of deciphering the multi-scale/physics structure/ionic transport correlations within TILCs. To realize these intertwined tasks, She/He will benefit from SoA Lab. (UMR5819-SyMMEs lab ) and European (ESRF , ILL , Soleil ) large-scale facilities dedicated (in situ/operando) characterizing multi-modal/physics platforms, making use of and/or combining: High Resolution & Solid-State NMR (HR-NMR & SS-NMR) and FTIR spectroscopies, Differential Scanning Calorimetry (DSC), Polarized Optical Microscopy (POM), Synchrotron-based X-ray Scattering (SAXS/WAXS) and Imaging (Tomography) Techniques, Cyclic Voltammetry (CV), Potentiostatic Electrochemical Impedance Spectroscopy (PEIS), Pulse-Field Gradient NMR (PFG-NMR), and NMR relaxometry, to name a few.
Under the co-supervision of Dr. P. Rannou (ORCID: 0000-0001-9376-7136 . PR’s Homepage :) and Dr. M. Marechal (ORCID: 0000-0002-4295-7244 . MM’s Homepage ) at the UMR5819-SyMMEs lab Grenoble, the PhD candidate will be embedded within the CNRS team of a recently granted 3 year-long H2020 project (Topic: LC-BAT-14-2020: “Self-healing functionalities for long lasting battery cell chemistries”. Type of Action: RIA. Budget: € 4,000,000. Starting date: Sept. 1, 2020) gathering the cross-fertilizing expertise and know-how of Seven partners across Europe within the Battery 2030+ European Initiative (https://battery2030.eu/ ).
Within this rich ((Electro)Chemistry, Physics, Nano-Science/Technologies, Nano-Ionics/Fluidics) and multinational environment, He/She will be strongly involved in the highly versatile and comprehensive tasks of a H2020 project, benefiting from interactions (and short stays & specific training action) within an unique research and innovation ecosystem consisting in Academic labs, SMEs, Research & Technology Organisations (RTOs specialized in Technology Transfer & Industry-oriented Research & Innovation), and Battery Manufacturers at the forefront of “beyond SoA” functional soft-matter and electrochemical energy storage research & innovation to develop her/his PhD project and to expand her/his professional network
Further reading (Topics : Functional Liquid Crystals, Nanoconfined Ionic Transport, Precision Copolymer Electrolytes, Solid Polymer Electrolytes, TILCs-based Electrolytes): Selected articles & patents over the 2014-2019 period
*1. Cherian, T.; Rosa Nunes, D.; Dane, T.G.; Jacquemin, J.; Vainio, U.; Myllymäki, T.; Timonen, J.; Houbenov, N.; Maréchal, M.; Rannou, P.; Ikkala, O. "Supramolecular self-assembly of nanoconfined ionic liquids for fast anisotropic ion transport", Adv. Funct. Mater.29, 1905054 (2019). DOI: 10.1002/adfm.201905054
*2. Myllymäki, T.T.T.; Guliyeva, A.; Korpi, A.; Kostiainen, M.A.; Hynninen, V.; Nonappa; Rannou, P.; O. Ikkala; O., Halila, S. "Lyotropic liquid crystals and linear supramolecular polymers of end-functionalized oligosaccharides", Chem. Commun. 55, 11739-11742 (2019), DOI: 10.1039/C9CC04715H
*3. Overton, P.; Rannou, P.; Picard L. “Sulfonamide macromolecules useful as single-ion conducting polymer electrolytes”, FR3068693, WO/2019/008061, Jan. 10, 2019. PCT/EP2018/068135
*4. Trigg, E.B.; Gaines, T.W.; Maréchal, M.; Moed, D.E.; Rannou, P.; Wagener, K.B.; Stevens, M.J.; Winey, K.I. “Self-Assembled highly ordered acid layers in precisely sulfonated polyethylene produce efficient proton transport”, Nat. Mater.17, 725-731 (2018). DOI: 10.1038/s41563-018-0097-2
*5. Delhorbe, V.; Bresser, D.; Mendil-Jakani, H.; Rannou , P.; Bernard, L.; Gutel, T.; Lyonnard, S.; Picard, L. “Unveiling the ion conduction mechanism in imidazolium-based poly(ionic liquids): A comprehensive investigation of the structure-to-transport interplay”, Macromolecules50, 4309-4321 (2017). DOI: 10.1021/acs.macromol.7b00197
*6. Picard, L.; Gebel, G.; Leclère, M.; Mendil-Jakani, H.; Rannou, P., “Electrolytes for electrochemical generators”, FR3041358, US20180261886, EP3353262, WO/2017/050769, March 30, 2017. PCT/EP2016/072312
*7. Ikkala, O.; Houbenov, N.; Rannou, P., "From block copolymer self-assembly, liquid crystallinity, and supramolecular concepts to functionalities", Handbook of Liquid Crystals (8 volumes), 2nd edition, Eds. J.W. Goodby, P.J. Collings, T. Kato, C. Tschierske, H. Gleeson, P. Raines, ISBN-13: 978-3-527-32773-7, Wiley-VCH, Weinheim, Germany, Volume 7: Supramolecular and Polymer Liquid Crystals, 541-598 (2014). DOI: 10.1002/9783527671403.hlc122
1: Thermotropic ionic liquid crystals (TILCs).
2: Self-Healing Electrolytes.
3: Lithium Metal Batteries (LMBs)
4: Nanoconfined Ionic Transport: NanoIonics/Nanofluidics.
5: Multi-scale/physics structure/Ionic transport correlations.
6: In situ vs. operando SoA multimodal characterizations within Lab. (SyMMES) & (Synchroton-based) large-scale facilities (i.e. ESRF/Soleil.)
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