Polymer Electrolyte Based on Cyano-Functionalized Polysiloxane with Enhanced Salt Dissolution and High Ionic ConductivityClick to copy article linkArticle link copied!
- Shuyi XieShuyi XieMaterials Research Laboratory, University of California, Santa Barbara, California 93106, United StatesMitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United StatesMore by Shuyi Xie
- Andrei NikolaevAndrei NikolaevMitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United StatesDepartment of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United StatesMore by Andrei Nikolaev
- Oscar A. NordnessOscar A. NordnessMaterials Research Laboratory, University of California, Santa Barbara, California 93106, United StatesMitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United StatesMore by Oscar A. Nordness
- Luana C. LlanesLuana C. LlanesMitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United StatesDepartment of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United StatesMore by Luana C. Llanes
- Seamus D. JonesSeamus D. JonesMitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United StatesDepartment of Chemical Engineering, University of California, Santa Barbara, California 93106, United StatesMore by Seamus D. Jones
- Peter M. RichardsonPeter M. RichardsonMaterials Research Laboratory, University of California, Santa Barbara, California 93106, United StatesMitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United StatesMore by Peter M. Richardson
- Hengbin WangHengbin WangMitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United StatesMore by Hengbin Wang
- Raphaële J. Clément*Raphaële J. Clément*Email: [email protected]Materials Research Laboratory, University of California, Santa Barbara, California 93106, United StatesMitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United StatesMaterials Department, University of California, Santa Barbara, California 93106, United StatesMore by Raphaële J. Clément
- Javier Read de Alaniz*Javier Read de Alaniz*Email: [email protected]Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United StatesMore by Javier Read de Alaniz
- Rachel A. Segalman*Rachel A. Segalman*Email: [email protected]Materials Research Laboratory, University of California, Santa Barbara, California 93106, United StatesMitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, California 93106, United StatesDepartment of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United StatesDepartment of Chemical Engineering, University of California, Santa Barbara, California 93106, United StatesMaterials Department, University of California, Santa Barbara, California 93106, United StatesMore by Rachel A. Segalman
Abstract

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.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 9 publications.
- 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
- 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
- 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
- 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
- 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
- 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
- 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
- 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
- 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
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.