Patrice Rannou 15mars2023

PCM Seminar - Dr Patrice RANNOUMercredi , 11h00 - Amphi IPREM

Le 15 mars 2023

Dr Patrice RANNOU
CNRS Director of Research
Laboratory of Electrochemistry and Physicochemistry of Materials and Interfaces
MIEL (Materials, Interfaces, and ELectrochemistry) Team
(UMR5279-LEPMI , CNRS/Grenoble-INP/Univ. Grenoble Alpes/Univ. Savoie Mont-Blanc)

 

"Bottlebrush Solid Polymer Electrolytes (BSPEs): Macromolecular design meets function to enable safer-by-design and performance in high-energy density Alkali-Metal Solid-State Batteries (AMSSBs)"

Abstract:
Addressing the (ever) increasing energy demand of the 21st century for electrical mobility (e-mobility) and portable/electronic devices requires radically new strategies towards safer-by-design and higher performance (post-Lithium-ion batteries (LiBs) with conventional (liquid/gel) electrolyte: Nobel Prize in Chemistry 2019[1]) electrochemical energy storage 2.0 solutions. Within this context, developing sustainable, safer, and higher energy density solid-state batteries[2] (SSBs) appears as one promising path to contribute fulfilling the United Nation Sustainable Development Goal N°7[3]. This acute societal need creates simultaneously scientific and technological challenges and opportunities for triggering innovation breakthroughs to allow the advent of (the much awaited) transformative technologies going well-beyond state-of-the-art (SoA) LiBs. To do so, two research endeavors can be synergistically pursued (i) moving from graphite toward alkali-metal-based negative electrodes, and (ii) replacing conventional organic electrolytes by solid-state (inorganic or polymer or nanocomposite) analogs through developing advanced (e.g. self-healing[4-6]) electrolytes[7-9] with extended electrochemical stability windows (ESW). While the former is inherently opening door to higher energy density SSBs (providing a smart control of key-enabling electrochemical processes at the reactive metals/electrolyte interface is obtained and efficient mitigation strategies developed to control the nucleating and growth of alkali metal dendrites), the latter could allow the use of higher potential positive electrodes to attain the same goal as well as enabling safer electrochemical energy storage solutions. Closing the loop toward an ultimate circular battery economy[10-12] will additionally require mass-production and efficient recycling techniques to ensure the smartest use of (critical/strategic) raw materials within these batteries 2.0

A century after the seminal work of Prof. Hermann Staudinger[13] and nearly five decades since the conception of alkali metal cation (e.g. Li+, Na+, K+) transport through a poly(ethylene oxide) (PEO) polymeric host matrix, we will exemplify how precise macromolecular engineering (i.e. design rules and syntheses) can be instrumental in designing beyond SoA salt-in-polymer (SiP) solid polymer electrolytes (SPEs)[14-18] to enable SSBs[2]. We will present in particular the design, synthesis & multi-scale structure/ionic conductivity correlations of functional polymeric bottlebrushes[19] (PPFS-g-PEO vs. PPFS-g-PTMC) consisting in a poly(2,3,4,5,6-pentafluorostyrene) (PPFS) backbone and methoxyPoly(ethylene gycol) (mPEG) vs. poly(trimethylene carbonate) (PTMC) side-chains acting as host matrices for lithium salts within the context of SiPSPEs based on PEO vs. PTMC. Highlighting the benefits of the "grating-onto" route[19-20] toward this macromolecular design making uses of (i) PPFS prepolymers[21] and (ii) hemitelechelic mPEG (commercially available) and PTMC (synthesized through organocatalyzed controlled ring-opening polymerization (ROP) of TMC) sub-blocks of controlled molar masses assembled through an organocatalyzed para-fluoro-thiol click (SNAr: nucleophilic aromatic substitution) reaction[22-23], the chemical, electrochemical (CV, LSV, and EIS), physical (EIS: ionic and Li+ conductivity), and thermal (DSC & TGA) characterizations of these bottlebrush solid polymer electrolytes (BSPEs[24-25]) will be presented; their electrochemical performances (ESW, LTN, and conductivity) being benchmarked with respect to PEO vs. PTMC-based (homopolymer) SiPSPEs[14-18]. In closing, we will (i) discuss tentative synthetic pathways towards single-ion bottlebrush solid polymer electrolytes (SIBSPEs), (ii) perform a side-by-side comparison of pros and cons of salt-in-polymer vs. single-ion bottlebrush solid polymer electrolytes (SiPBSPEs vs. SIBSPEs), and (iii) elaborate on the scope of BSPEs for enabling sustainable[9-11] and smart[4-6] high performance alkali metal-based solid-state batteries (AMSSBs).

Acknowledgments
Dr. P. Rannou acknowledges CNRS, Univ. Grenoble Alpes (UGA), Grenoble-INP, and the French National Agency of Research (ANR) for scientific and financial supports to research conducted within the CHARTREUSE (International Strategic Project (ISP2017) of Idex-UGA: ProjetIA-15-IDEX-0002) and REACT (ANR-15-PIRE-0001) projects.

References
[1]: Nobel Prize in Chemistry 2019. [2]: Nat. Energy (2023). DOI: 10.1038/s41560-023-01208-9. [3]: UN SDG N°7. [4]: Adv. Energy. Mater. 10, 2002815 (2020). DOI: 10.1002/aenm.202002815. [5]: Adv. Energy. Mater. 12, 2102652 (2022). DOI: 10.1002/aenm.202102652. [6]: Chem. Rev. (2022). DOI: 10.1021/acs.chemrev.2c00231. [7]: Adv. Energy Mater. 12, 2201264 (2022). DOI: 10.1002/aenm.202201264. [8]: ACS Polym. Au (2022). DOI: 10.1021/acspolymersau.2c00024. [9]: Science 378, eabq3750 (2022). DOI: 10.1126/science.abq3750. [10]: Adv. Energy Sustainability Res. 2, 2100047 (2021). DOI: 10.1002/aesr.202100047. [11]: Nat. Electron. 5, 5 (2022). DOI: 10.1038/s41928-021-00711-9. [12]: Joule 6, 1743 (2022). DOI: 10.1016/j.joule.2022.06.022. [13]: Giant 4, 100036 (2020). DOI: 10.1016/j.giant.2020.100036. [14]: J. Mater. Chem. A 3, 19218 (2015). DOI: 10.1039/C5TA03471J. [15]: Adv. Sci. 8, 2003675 (2021). DOI: 10.1002/advs.202003675. [16]: Prog. Polym. Sci. 116, 101453 (2021). DOI: 10.1016/j.progpolymsci.2021.101453. [17]: Chem. Commun. 58, 8182 (2022). DOI: 10.1039/d2cc02306g. [18]: Mater. Futures 1, 042103 (2022). DOI: 10.1088/2752-5724/ac9e6b. [19]: Prog. Polym. Sci. 116, 101387 (2021). DOI: 10.1016/j.progpolymsci.2021.101387. [20]: FR3107274, EP3865532, US20210253760, CN113265055. [21]: FR3099648, EP3763748. [22]: Nobel Prize in Chemistry 2022. [23]: Polym. Chem. 9, 2679 (2018). DOI: 10.1039/C8PY00287H. [24]: FR3107276, EP3865533, US20210296699, CN113270638. [25]: ACS Appl. Energy Mater. 5, 15520 (2022). DOI: 10.1021/acsaem.2c03089

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