Research ArticleNANOMATERIALS

Hierarchical multiscale hyperporous block copolymer membranes via tunable dual-phase separation

See allHide authors and affiliations

Science Advances  24 Jul 2015:
Vol. 1, no. 6, e1500101
DOI: 10.1126/sciadv.1500101
  • Fig. 1 Schematic illustration showing the fabrication and physical appearance of HMH-BCP membranes.

    Bottom left: Nucleophilic substitution reaction between the pyridine moiety of the PS-b-P4VP and the surface energy–modifying agent GPTMS to generate PS-b-G-P4VP. Subsequent solvent-nonsolvent exchange leads to macro/nano-phase separation to form the hierarchical multiscale hyperporous structure.

  • Fig. 2 Structural uniqueness of HMH-BCP membranes.

    (A to D) Cross-sectional SEM images showing hyperporous membranes with micro- and nanopores over the entire film thickness direction. (B to D) Magnified images of the rectangular boxes shown in (A). (E) TEM image of an HMH-BCP thin film fabricated from 1 wt % PS-b-G-P4VP solution. (F) HAADF-STEM image taken from the green box shown in (E). (G) EDS line-scan profile and point spectrum taken from the yellow line and point in the STEM image shown in (F). cps, counts per second.

  • Fig. 3 Effect of GPTMS content (determined by the reaction time) on morphology (cross-sectional SEM image) of PS-b-G-P4VP membranes.

    (A to D) GPTMS substitution reaction time: (A) 0 min (bare PS-b-P4VP), (B) 30 min, (C) 40 min, and (D) 120 min. (E to H) Magnified views of the SEM images shown in (A) to (D). (I) Change in Si content (corresponding to GPTMS) of PS-b-G-P4VP with GPTMS substitution reaction time. (J) Change in water contact angle of PS-b-G-P4VP thin films with GPTMS substitution reaction time.

  • Fig. 4 Application of HMH-BCP membrane to a LIB separator versus a commercial PP/PE/PP separator as a control sample.

    (A) Charge/discharge rate capabilities of the HMH-BCP membrane [1st to 15th cycles: under a fixed charge current density (0.5 C) and various discharge current densities (0.5 to 5.0 C); 16th to 27th cycles: under a fixed discharge current density (0.5 C) and various charge current densities (0.5 to 3.0 C)]. (B) Cycling performance at high charge/discharge current densities (1.0/1.0 C, 2.0/2.0 C) at room temperature. (C) Long-term cycling performance (charge/discharge current density, 1.0/1.0 C) at 50°C. All cells were cycled in the voltage range of 1.5 to 2.8 V. (D) TOF-SIMS analysis of the separators before and after high-temperature cycling test (200 cycles). a.u., arbitrary units.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/1/6/e1500101/DC1

    Materials and Methods

    Fig. S1. FTIR spectra of PS-b-P4VP and PS-b-G-P4VP films.

    Fig. S2. Surface morphologies of top and bottom surfaces of the HMH-BCP membrane.

    Fig. S3. Quantitative analysis of pore size distribution of the HMH-BCP membrane (GPTMS substitution reaction at 120°C for 30 min) using mercury intrusion porosimetry.

    Fig. S4. Structural characterization of the microtomed HMH-BCP membrane (GPTMS substitution reaction at 120°C for 30 min).

    Fig. S5. TOF-SIMS data of bare PS-b-P4VP and HMH-BCP membranes.

    Fig. S6. Cross-sectional SEM images of a bare PS-b-P4VP membrane showing a sponge-like structure.

    Fig. S7. Structural characterization of the PS-b-G-P2VP membrane.

    Fig. S8. Structural characterization of the HMH-BCP (PS-b-G-P2VP) membrane (GPTMS substitution reaction at 120°C for 6 hours).

    Fig. S9. Cross-sectional SEM images of PS-b-G-P4VP membranes (GPTMS substitution reaction at 120°C for 20 min).

    Fig. S10. A conceptual ternary phase diagram of PS-b-G-P4VP membranes as a function of GPTMS substitution time.

    Fig. S11. Cross-sectional SEM images of PS-b-G-P4VP membranes fabricated from ethanol and water nonsolvents.

    Fig. S12. Characterization of PS-b-G-P4VP membranes fabricated as a function of drying time at 110°C.

    Fig. S13. Characterization of internal cell resistance of HMH-BCP membrane and PP/PE/PP separator.

    Fig. S14. Structural analysis of separator membranes after cycling test (200 cycles at charge/discharge current density of 1 C/1 C) at high temperature (50°C).

    Fig. S15. Height mode AFM image of pure PS-b-P4VP copolymer thin films annealed in chloroform vapor.

    References (3437)

  • Supplementary Materials

    This PDF file includes:

    • Materials and Methods
    • Fig. S1. FTIR spectra of PS-b-P4VP and PS-b-G-P4VP films.
    • Fig. S2. Surface morphologies of top and bottom surfaces of the HMH-BCP membrane.
    • Fig. S3. Quantitative analysis of pore size distribution of the HMH-BCP membrane (GPTMS substitution reaction at 120°C for 30 min) using mercury intrusion porosimetry.
    • Fig. S4. Structural characterization of the microtomed HMH-BCP membrane (GPTMS substitution reaction at 120°C for 30 min).
    • Fig. S5. TOF-SIMS data of bare PS-b-P4VP and HMH-BCP membranes.
    • Fig. S6. Cross-sectional SEM images of a bare PS-b-P4VP membrane showing a sponge-like structure.
    • Fig. S7. Structural characterization of the PS-b-G-P2VP membrane.
    • Fig. S8. Structural characterization of the HMH-BCP (PS-b-G-P2VP) membrane (GPTMS substitution reaction at 120°C for 6 hours).
    • Fig. S9. Cross-sectional SEM images of PS-b-G-P4VP membranes (GPTMS substitution reaction at 120°C for 20 min).
    • Fig. S10. A conceptual ternary phase diagram of PS-b-G-P4VP membranes as a function of GPTMS substitution time.
    • Fig. S11. Cross-sectional SEM images of PS-b-G-P4VP membranes fabricated from ethanol and water nonsolvents.
    • Fig. S12. Characterization of PS-b-G-P4VP membranes fabricated as a function of drying time at 110°C.
    • Fig. S13. Characterization of internal cell resistance of HMH-BCP membrane and PP/PE/PP separator.
    • Fig. S14. Structural analysis of separator membranes after cycling test (200 cycles at charge/discharge current density of 1 C/1 C) at high temperature (50°C).
    • Fig. S15. Height mode AFM image of pure PS-b-P4VP copolymer thin films annealed in chloroform vapor.
    • References (34–37)

    Download PDF

    Files in this Data Supplement:

Navigate This Article