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Polymer Electrolyte Based on Cyano-Functionalized Polysiloxane with Enhanced Salt Dissolution and High Ionic Conductivity
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    Polymer Electrolyte Based on Cyano-Functionalized Polysiloxane with Enhanced Salt Dissolution and High Ionic Conductivity
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    • Shuyi Xie
      Shuyi Xie
      Materials Research Laboratory, University of California, Santa Barbara, California 93106, United States
      Mitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United States
      More by Shuyi Xie
    • Andrei Nikolaev
      Andrei Nikolaev
      Mitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United States
      Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States
    • Oscar A. Nordness
      Oscar A. Nordness
      Materials Research Laboratory, University of California, Santa Barbara, California 93106, United States
      Mitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United States
    • Luana C. Llanes
      Luana C. Llanes
      Mitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United States
      Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States
    • Seamus D. Jones
      Seamus D. Jones
      Mitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United States
      Department of Chemical Engineering, University of California, Santa Barbara, California 93106, United States
    • Peter M. Richardson
      Peter M. Richardson
      Materials Research Laboratory, University of California, Santa Barbara, California 93106, United States
      Mitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United States
    • Hengbin Wang
      Hengbin Wang
      Mitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United States
      More by Hengbin Wang
    • Raphaële J. Clément*
      Raphaële J. Clément
      Materials Research Laboratory, University of California, Santa Barbara, California 93106, United States
      Mitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United States
      Materials Department, University of California, Santa Barbara, California 93106, United States
      *Email: [email protected]
    • Javier Read de Alaniz*
      Javier Read de Alaniz
      Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States
      *Email: [email protected]
    • Rachel A. Segalman*
      Rachel A. Segalman
      Materials Research Laboratory, University of California, Santa Barbara, California 93106, United States
      Mitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United States
      Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States
      Department of Chemical Engineering, University of California, Santa Barbara, California 93106, United States
      Materials Department, University of California, Santa Barbara, California 93106, United States
      *Email: [email protected]
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    Macromolecules

    Cite this: Macromolecules 2022, 55, 13, 5723–5732
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    https://doi.org/10.1021/acs.macromol.2c00329
    Published June 21, 2022
    Copyright © 2022 American Chemical Society

    Abstract

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    Polymer electrolytes (PEs) offer a promising avenue toward safer, more mechanically robust and high power density lithium-ion batteries. In PEs, conduction is achieved through the dissolution and subsequent transport of the lithium cation and organic anion, yet only lithium transport provides useful current between the two electrodes and must be maximized. As such, PEs are rationally designed to include solvation groups that only moderately interact with the Li+ cations to enable high ionic conductivity (σ) and a high Li+ transference number (t+). Herein, we report a polysiloxane-based PE grafted with cyano-containing side chains that exhibits a total ionic conductivity of 6.9 × 10–4 S/cm and a Li+ transference number of 0.48 at 90 °C, demonstrating significant performance improvements compared to the typical poly(ethylene oxide) (PEO) benchmark. Wide-angle X-ray scattering data indicate that there is no ion aggregation in these systems up to a salt loading of r = [Li+]/[CN] = 0.3. The high ion dissolution ability of the present PE is attributed to its high dielectric permittivity and the modest Li+-side-chain interaction due to the introduction of the polar cyano group, as probed by electrochemical impedance spectroscopy and infrared/Raman spectroscopy, respectively. Moreover, the side-chain length is critical to ion transport and cation selectivity. With a short alkyl chain length, the polymer matrix effectively solvates salt ions and offers good cation selectivity, while the ion mobility is limited by the chain rigidity; with a longer chain length, the polymer segmental motion increases, while the salt dissolution ability drops and the polymer is less cation-selective. These results demonstrate the vast potential of nonpolar flexible polymers grafted with polar side chains as host materials for PEs.

    Copyright © 2022 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.macromol.2c00329.

    • SEC trace for the PVMS precursor; synthesis details and NMR spectra for PMS-5-CN, PMS-9-CN, and PMS-16-CN; Nyquist plot for the salt-free polymer; small-angle X-ray scattering profiles for salt-doped PMS-9-CN; diffusion coefficients and solid-state NMR fitting; and optical images of salt-doped polymer electrolytes (PDF)

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    This article is cited by 9 publications.

    1. James T. Bamford, Leo W. Gordon, Raphaële J. Clément, Rachel A. Segalman. Converting a Metal-Coordinating Polymer to a Polymerized Ionic Liquid Improves Li+ Transport. ACS Macro Letters 2025, 14 (1) , 87-92. https://doi.org/10.1021/acsmacrolett.4c00704
    2. Yuqing Zhao, Simi Sui, Qian Yang, Jiaxin Li, Shenxu Chu, Mengjia Gu, Lin Li, Shuo Shi, Yu Zhang, Zhuo Chen, Shulei Chou, Kaixiang Lei. Electrolyte-Induced Morphology Evolution to Boost Potassium Storage Performance of Perylene-3,4,9,10-tetracarboxylic Dianhydride. Nano Letters 2024, 24 (15) , 4546-4553. https://doi.org/10.1021/acs.nanolett.4c00590
    3. Gordon Pace, Alexandra Zele, Phong Nguyen, Raphaële J. Clément, Rachel A. Segalman. Mixed Ion–Electron-Conducting Polymer Complexes as High-Rate Battery Binders. Chemistry of Materials 2023, 35 (19) , 8101-8111. https://doi.org/10.1021/acs.chemmater.3c01587
    4. Gordon Pace, Oscar Nordness, Phong H. Nguyen, Yu-Jin Choi, Cassidy Tran, Raphaële J. Clément, Rachel A. Segalman. Tuning Transport via Interaction Strength in Cationic Conjugated Polyelectrolytes. Macromolecules 2023, 56 (15) , 6078-6085. https://doi.org/10.1021/acs.macromol.3c01206
    5. Chenxiao Yin, Jingrui Sun, Chang Cui, Ke‐Ke Yang, Ling‐Ying Shi, Yiwen Li. Chaotropic Ions Mediated Polymer Gelation for Thermal Management. Advanced Science 2024, 11 (32) https://doi.org/10.1002/advs.202405077
    6. Qian Zhang, Jing Wei, JinYuan Zhao, Jian Wang, Chunjie Ma, Junpeng Li, Yaping Du. Silane-modified HMMM gel polymer electrolyte with wide electrochemical window and high flame retardance for lithium metal battery. Journal of Electroanalytical Chemistry 2024, 967 , 118465. https://doi.org/10.1016/j.jelechem.2024.118465
    7. Asish K. Sahu, K.S.K. Varadwaj, Sanjay K. Nayak, Smita Mohanty. Single-ion conducting polymer electrolyte: A promising electrolyte formulation to extend the lifespans of LMBs. Nano Energy 2024, 122 , 109261. https://doi.org/10.1016/j.nanoen.2024.109261
    8. Nicolas Goujon, Itziar Aldalur, Alexander Santiago, Michel Armand, Maria Martinez-Ibañez, Heng Zhang. Opportunity for lithium-ion conducting polymer electrolytes beyond polyethers. Electrochimica Acta 2024, 480 , 143909. https://doi.org/10.1016/j.electacta.2024.143909
    9. Faruk Okur, Yauhen Sheima, Can Zimmerli, Huanyu Zhang, Patrick Helbling, Ashling Fäh, Iacob Mihail, Jacqueline Tschudin, Dorina M. Opris, Maksym V. Kovalenko, Kostiantyn V. Kravchyk. Nitrile‐functionalized Poly(siloxane) as Electrolytes for High‐Energy‐Density Solid‐State Li Batteries. ChemSusChem 2024, 17 (3) https://doi.org/10.1002/cssc.202301285

    Macromolecules

    Cite this: Macromolecules 2022, 55, 13, 5723–5732
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.2c00329
    Published June 21, 2022
    Copyright © 2022 American Chemical Society

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