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Chain dimensions of poly(ethylene carbonate/ethylene oxide) copolymer with salt addition studied by SANS

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Abstract

In this study, we investigated polymer chain dimensions in solid polymer electrolytes (SPEs) composed of hydrogenated and deuterated poly(ethylene carbonate/ethylene oxide) (h-/d-P(EC/EO)) copolymers and lithium bis(trifluoromethane)sulfonimide (LiTFSI) at various lithium-ion concentrations. The results were compared with h/d-poly(ethylene oxide) (PEO)/LiTFSI systems, extensively studied for their ionic conduction properties. The scattering intensity I(q) at low scattering vector q (≤ 0.4 Å−1) decreased with increasing lithium-ion concentration. From the low q data, the radius of gyration Rg of the polymer chains in SPE was estimated by the Guinier method. For both PEO and P(EC/EO) systems, with increasing the lithium-ion concentration (i.e., molar ratio of lithium ion to monomer, rs), Rg(rs) first decreased and then increased. Furthermore, the normalized Rg(rs) by Rg(0) exhibited a minimum at rs ≈ 0.15 for the PEO systems, whereas the P(EC/EO) system displayed a decrease in Rg to a higher rs (≈ 0.20) followed by a weak re-increase. Previous MD simulations (Y. Doi, et al., J. Phys. Chem. C2022, 126, 20,284) in the P(EC/EO)/LiTFSI systems have reported preferential coordination of carbonyl oxygens to lithium ions and an increase in the coordination number of oxygen atoms (resulting in the disrupted coordination structure) compared to the corresponding PEO systems, which can well explain the results in this study. The above experimental facts in this study are important findings in that they include data on new polymer systems other than PEO, while the number of reports for polymer conformation studies of SPE systems by SANS is still limited.

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Acknowledgements

SANS measurements at J-PARC were carried out with Proposal No. 2020A0040, 2020B0009, and 2022B0055 at BL-15, and the authors thank Dr. Hiroki Iwase (CROSS) for his technical support.

Funding

This study is partly supported by the Ogasawara Toshiaki Memorial Foundation, Yazaki Memorial Foundation for Science and Technology, ENEOS Tonen General Research/Development Encouragement & Scholarship Foundation, the Naito Science & Engineering Foundation, Toyoaki Scholarship Foundation, Amano Institute of Technology, Iwatani Naoji Foundation and Research Foundation for the Electrotechnology of Chubu, and the first author (Y.D.) acknowledges them.

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Authors and Affiliations

  1. Department of Materials Physics, Nagoya University, Nagoya, Aichi, 4648603, Japan

    Yuya Doi

  2. Jülich Centre for Neutron Science (JCNS), Forschungszentrum Jülich GmbH, Jülich, 52425, Germany

    Yuya Doi, Jürgen Allgaier, Stephan Förster & Michael Ohl

  3. Department of Organic Materials Science, Yamagata University, Yonezawa, Yamagata, 992-5810, Japan

    Yuya Doi

  4. J-PARC Center, Japan Atomic Energy Agency (JAEA), Tokai, Ibaraki, 319-1195, Japan

    Shin-ichi Takata

Authors
  1. Yuya Doi
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  2. Jürgen Allgaier
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  3. Stephan Förster
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  4. Shin-ichi Takata
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  5. Michael Ohl
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Contributions

All authors contributed to the conceptualization of this study. Y.D. synthesized and characterized the samples, performed SANS measurements, analyzed the SANS data, and written the original manuscript. J.A. synthesized and characterized the samples. S.F. has supervised. S.T. was the local contact during the SANS beam time and gave suggestions for the SANS data treatment. M.O. has supervised, discussed the data, and revised the manuscript. All authors read and approved the manuscript.

Corresponding authors

Correspondence to Yuya Doi or Michael Ohl.

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The authors declare no competing interests.

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Special issue dedicated to the occasion of the 60th birthday of Stephan Förster.

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Appendices

Appendix 1. Treatment of incoherent scattering

As described in experimental, the main component of incoherent scattering in the raw SANS profile was assumed to be from the protonated polymer in the sample. Thus, the coherent scattering intensity, Icoh(q), shown in the main text is estimated by subtracting the incoherent contribution (Iincoh(q) = Φh-polymIh-polym(q), where Φh-polym denotes the volume fraction of hydrogenated polymer in the sample) from the raw data, Iraw(q). Figure 5 shows the scattering profiles before and after subtracting the incoherent scattering for h/d-P(EC/EO)/LiTFSI samples with different wLi (= 0 and 0.33). In the high q region, LiTFSI in addition to the hydrogenated polymers may work as an incoherent component, but at least in the low q (≤ 0.1 Å−1) region discussed in the main text, our incoherent scattering treatment has little effect on the main conclusion of this study.

Fig. 5
figure 5

ANS profile before and after subtracting the incoherent scattering for h/d-P(EC/EO)/LiTFSI with wLi = a 0 and b 0.33

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Appendix 2. Volume fraction dependence of I(0)

In Figs. 2a and 3a in the text, we have applied the Guinier approximation to obtain I(0) as well as Rg for the PEO/LiTFSI and P(EC/EO)/LiTFSI systems for different wLi. In principle, I(0)s obtained there should reflect the molecular weight and fraction of polymers as scatterers. Figure 6 shows the dependence of I(0) on the polymer volume fraction ΦP for PEO/LiTFSI and P(EC/EO)/LiTFSI. In Fig. 6, a good proportional relationship with zero intercept is obtained for both PEO/LiTFSI and P(EC/EO)/LiTFSI, although there is some variance in the data. At the same ΦP, I(0) is higher for the P(EC/EO) system than for the PEO one, mainly because the former has a higher molecular weight, which is correlated with scattering ability.

Fig. 6
figure 6

ΦP-dependence of I(0) estimated from the Guinier approximation for PEO/LiTFSI and P(EC/EO)/LiTFSI. The lines indicate approximate straight ones with zero intercept

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Doi, Y., Allgaier, J., Förster, S. et al. Chain dimensions of poly(ethylene carbonate/ethylene oxide) copolymer with salt addition studied by SANS. Colloid Polym Sci (2024). https://doi.org/10.1007/s00396-024-05279-2

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