Effect of crystallization of the polyhedral oligomeric silsesquioxane block on self-assembly in hybrid organic-inorganic block copolymers with salt

[EN] We present a DSC and X-ray scattering study investigating the effect of polyhedral oligomeric silsesquioxane (POSS) block crystallinity on the self-assembly of a poly(acryloisobutyl polyhedral oligomeric silsesquioxane)- b -poly(ethylene oxide)- b -poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (POSS-PEO-POSS) triblock copolymer and poly(ethylene oxide)- b - poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO-POSS) diblock copolymers mixed with lithium bis(trifluoromethanesulfonyl)imide salt. The POSS block in all copolymer/salt mixture organizes into a rhombohedral crystal, similar to that of the POSS homopolymer. Semicrystalline polymer/salt mixtures favor morphologies with flat interfaces ( i.e ., lamellae) despite the asymmetric nature of the copolymers; PEO/salt volume fractions range from 0 to 0.85. Coexisting lamellae and hexagonally packed cylinders as well as coexisting lamellae with different domain spacings are seen in many copolymer/salt mixtures wherein the POSS block is amorphous. Morphological phase transitions in these systems are seen in the vicinity of the POSS crystallization temperature.This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract DE-AC02- 05CH11231 under the Battery Materials Research Program. X-ray work performed at Advanced Light Source, which is a DOE Office of Science User Facility, was supported by Contract No. DE-AC02- 05CH11231 . X-ray work performed at the Stanford Synchrotron Radiation Light Source, a user facility at SLAC National Accelerator Laboratory, was supported by the U.S. Department of Energy , Office of Science, Office of Basic Energy Sciences under Contract No. DE- AC02-76SF00515 . Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE- AC02-05CH11231 . G.K.S. acknowledges funding from a National Science Foundation Graduate Student Research Fellowship

Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries

This study describes hybrid single ion-conducting electrolytes based on inorganic sulfide glasses and perfluoropolyether polymers for lithium batteries. Herein, it is shown that hybrid electrolytes provide a compelling alternative to the traditional glass, ceramic, or polymer battery electrolytes. These electrolytes present high transference numbers, unprecedented ionic conductivities at room temperature, and excellent electrochemical stability, and they limit the dissolution of lithium polysulfides. The results in this work represent a significant step toward addressing the challenges of enabling the next generation cathodes, such as lithium nickel manganese cobalt oxide and sulfur

Remodeling arteries: studying the mechanical properties of 3D-bioprinted hybrid photoresponsive materials.

3D-printed cell models are currently in the spotlight of medical research. Whilst significant advances have been made, there are still aspects that require attention to achieve more realistic models which faithfully represent the in vivo environment. In this work we describe the production of an artery model with cyclic expansive properties, capable of mimicking the different physical forces and stress factors that cells experience in physiological conditions. The artery wall components are reproduced using 3D printing of thermoresponsive polymers with inorganic nanoparticles (NPs) representing the outer tunica adventitia, smooth muscle cells embedded in extracellular matrix representing the tunica media, and finally a monolayer of endothelial cells as the tunica intima. Cyclic expansion can be induced thanks to the inclusion of photo-responsive plasmonic NPs embedded within the thermoresponsive ink composition, resulting in changes in the thermoresponsive polymer hydration state and hence volume, in a stimulated on-off manner. By changing the thermoresponsive polymer composition, the transition temperature and pulsatility can be efficiently tuned. We show the direct effect of cyclic expansion and contraction on the overlying cell layers by analyzing transcriptional changes in mechanoresponsive mesenchymal genes associated with such microenvironmental physical cues. The technique described herein involving stimuli-responsive 3D printed tissue constructs, also described as four- dimensional (4D) printing, offers a novel approach for the production of dynamic biomodels.Financial support is acknowledged from the MCIN/AEI/ 10.13039/501100011033 through grant # PID2019-108854RAI00. C. G. A. thanks to the Ministerio de Ciencia e Innovacio´n (MCIN) for a Juan de la Cierva Incorporacio´n Fellowship (IJC2019-040827-I). M. S.-A. is recipient of a Ramo´n y Cajal contract and a ‘‘Generacio´n de Conocimiento’’ grant from the Ministerio de Ciencia e Innovacio´n (RYC2020-029690-I and PID2021-128106NA-I00). MAdP is coordinator and PL of ‘‘AtheroConvergence’’ La Caixa Foundation Health Research consortium (HR20-00075). The CNIC is supported by the Instituto de Salud Carlos III (ISCIII), the MCIN and the Pro CNIC Foundation, and is a Severo Ochoa Center of Excellence (grant CEX2020-001041-S). We acknowledge ALBA for provision of synchrotron radiation facilities. We would like to thank Dr Marc Malfois for assistance in using BL11-NCD beamline, and Unai Cossı´o and Daniel Padro for help with image analysis.S

Interface studies in solid lithium metal batteries based on halide hybrid electrolytes

International audienceThe implementation of solid electrolyte as a component within all-solid-state battery is of great interest to develop the next generation of batteries. Indeed, this would enable the development of batteries with higher energy densities compared to the current Li-ion technology, and without flammable liquid organic electrolyte. Herein, hybrid solid base electrolyte (HSE) is presented and discussed, as the combination of both inorganic and polymer materialsin an attempt to overcome the drawbacks of each other and favor their synergy. [1] The study focuses on lithium indium chloride (LIC) that presents high ionic conductivity values exceeding mS/cm at room temperature and styrene-ethylene-butylene-styrene (SEBS) as a inert polymer binder, which provides flexibility to the system. [2,3] Nevertheless, this composition still meets some challenges, like instability with Li metal anode. Therefore, it is necessary not only to optimize the hybrid electrolyte formulation to reach high ionic conductivity and mechanical properties but also to tackle this interface issue.. Therefore, one strategy is to protect the Li electrode surface with a protective polymer electrolyte interlayer known to be stable with Li.The presentation will cover the investigation of the multilayer setup comprising HSE and poly(ethylene oxide)-based (PEO) protection layer in two-electrode cells with blocking (stainless steel) or reversible (Li) electrodes. We examine the transport properties by electrochemical methodologies such as impedance spectroscopy.[4] Impedance is a technic of choice as it permits to decompose in frequencies the different transport phenomena from the bulk of both conducting phase (HSE and PEO) as well as at the Li/PEO and PEO/HSE interfaces. This study is the first to move toward an optimized materials’ assembly suitable for a Li battery application. [1] Z. Cheng, T. Liu, B. Zhao, F. Shen, H. Jin, X. Han, Energy Storage Materials 34 (2021), 388–416[2] X. Li, J. Liang, N. Chen, J. Luo, K.R. Adair, Ch. Wang, M. Norouzi Banis, T-K. Sham, L. Zhang, S. Zhao, S. Lu, H. Huang, R. Li, X. Sun, Angew. Chem. Int. Ed. 58 (2019), 16427 –16432[3] D.H.S. Tan, A. Banerjee, Z. Deng, E.A. Wu, H. Nguyen, J.M. Doux, X. Wang, J. Cheng, S.P. Ong, Y.S. Meng, Z. Chen, ACS Appl. Energy Mater. 2 (2019), 6542−6550.[4] J.A. Isaac, L.R. Mangani, D. Devaux, R. Bouchet, ACS Appl. Mater. Interfaces 14 (2022), 13158−1316

Nanoparticle-Driven Assembly of Highly Conducting Hybrid Block Copolymer Electrolytes

International audienceHybrid nanostructured materials comprising block copolymers, nanoparticles, and lithium salts have the potential to serve as electrolytes in non-flammable rechargeable lithium batteries. Here we show that the addition of functionalized nanoparticles, at an optimized concentration, into lamellar block copolymer electrolytes, results in an increase in ionic conductivity. This is due to the occurrence of a lamellar-to-bicontinuous phase transition, driven by the addition of nanoparticles. The magnitude of the increase in conductivity is consistent with a simple model that accounts for the morphology of the conducting channels. The conductivity of the optimized hybrid electrolyte is only 6% lower than that of an idealized nanostructured electrolyte with perfectly connected conducting pathways and no dead ends

Nanoparticle-driven assembly of co-continuous block copolymer electrolytes

International audienc

X-Ray Microtomography Analysis of Li-Sulfur Batteries with a Block Copolymer Electrolyte

International audienceLi-ion batteries are the dominant solution for many applications, from small electronic devices up to hybrid and fully electric vehicles.[1] However, this technology is now mature and new chemistries are needed to reach high specific energy while ensuring safety. Despite a relatively low operating voltage, sulfur (S8) is an attractive cathode active material due to its high theoretical specific capacity; a factor of six higher than traditional LiCoO2 cathodes.[2] To realize high energy density systems, the S8 cathode must be paired with a Li metal anode. Many challenges remain to be addressed to effectively couple a Li metal with a S8 cathode such as the low S8 utilization, the strong volume change of active material upon cycling, the insulating nature of S8 and of the final product Li2S, the solubility of polysulfides in the electrolyte.[3] This issues lead to poor capacity retention, limited cycle life, and low Coulombic efficiency. To address the polysulfide dissolution problem one approach consists in confining S8 within mesoporous and nanoporous carbon.[4] However, conventional liquid electrolytes are not stable against Li metal. A solution is then to use a solid polymer electrolytes, such as polystyrene-b-poly(ethylene oxide) (SEO) block copolymer doped with LiTFSI salt, known to stabilize Li metal.[5]The goal of this study is to understand the behavior of Li-S8 batteries comprising a SEO electrolyte. The cathode is a composite made of carbon, SEO electrolyte and sulfur-impregnated carbon nanospheres.[6] The cells were cycled and exhibited significant capacity fade. We thus used hard X-ray microtomography to determine the reason for this capacity fade. Figure 1 represents tomography images prior and after cycling. In addition to polysulfide dissolution, our observations indicate that the battery failure in our system is also due to strong changes at the Li/SEO interface.References[1] J. B. Goodenough, K.-S. Park, J. Am. Chem. Soc., 135 (2013) 1167 (2013).[2] P. G. Bruce, S. A. Freunberger, L. J. Hardwick, J.-M. Tarascon, Nat. Mater., 11 (2012) 19.[3] S. S. Zhang, J. Power Sources, 231, 153 (2013).[4] X. Fan, W. Sun, F. Meng, A. Xing, J. Liu, Green Energy Environ., 3 (2018) 2.[5] D. T. Hallinan, S. A. Mullin, G. M. Stone, and N. P. Balsara, J. Electrochem. Soc., 160, (2013) A464.[6] D. Devaux, I. Villaluenga, X. Jiang, Y. H. Chang, D. Y. Parkinson, N. P. Balsara, J. Electrochem. Soc., 167 (2020) 06050