Improved Mechanical Strength without Sacrificing Li-Ion Transport in Polymer Electrolytes

Bamford, James1 ; Bamford, James T.2 ; Jones, Seamus D.3 ; Schauser, Nicole S.2; Pedretti, Benjamin J.4; Gordon, Leo W.2 ; Lynd, Nathaniel A.4 ; Clément, Raphaële J.2 ; Segalman, Rachel A.2

Research facility: University of California, Santa Barbara

Published Aug 14, 2024 on Dryad. https://doi.org/10.5061/dryad.5x69p8dd5

Data files

Aug 14, 2024 version files 1.02 MB

Abstract

Next-generation batteries demand solid polymer electrolytes (SPEs) with rapid ion transport and robust mechanical properties. However, many SPEs with liquid-like Li⁺ transport mechanisms suffer a fundamental trade-off between conductivity and strength. Dynamic polymer networks can improve bulk mechanics with minimal impact to segmental relaxation or ionic conductivity. This study demonstrates a system where a single polymer-bound ligand simultaneously dissociates Li⁺ and forms long-lived Ni²⁺ networks. The polymer comprises an ethylene oxide backbone and imidazole (Im) ligands, blended with Li⁺ and Ni²⁺ salts. Ni²⁺–Im dynamic cross-links result in the formation of a rubbery plateau resulting in, consequently, storage modulus improvement by a factor of 133× with the introduction of Ni²⁺ at r_Ni = 0.08, from 0.014 to 1.907 MPa. Even with Ni²⁺ loading, the high Li⁺ conductivity of 3.7 × 10^–6 S/cm is retained at 90 °C. This work demonstrates that decoupling of ion transport and bulk mechanics can be readily achieved by the addition of multivalent metal cations to polymers with chelating ligands.

README: Improved Mechanical Strength without Sacrificing Li-Ion Transport in Polymer Electrolytes

https://doi.org/10.5061/dryad.5x69p8dd5

Description of the data and file structure

GENERAL INFORMATION

1. Title of Dataset: Improved Mechanical Strength Without Sacrificing Li-ion Transport in Polymer Electrolytes

2. Author Information

A. Principal Investigator Contact Information

    Name: Rachel Segalman

    Institution: UC Santa Barbara

    Address: UC Santa Barbara, Santa Barbara, California 93106

    Email: segalman@ucsb.edu

B. Principal Investigator Contact Information

    Name: James T. Bamford

    Institution: UC Santa Barbara

    Address: UC Santa Barbara, Santa Barbara, California 93106

    Email: jbamford@ucsb.edu

C. Associate or Co-investigator Contact Information

    Name: Seamus D. Jones

    Institution: UC Santa Barbara

    Address: UC Santa Barbara, Santa Barbara, California 93106

    Email: sjones97@calpoly.edu

D. Associate or Co-investigator Contact Information

    Name: Nicole S. Schauser

    Institution: UC Santa Barbara

    Address: UC Santa Barbara, Santa Barbara, California 93106

    Email: nicole.schauser@gmail.com

E. Associate or Co-investigator Contact Information

    Name: Benjamin J. Pedretti

    Institution: UT Austin

    Address: Main Building (MAI), 110 Inner Campus Drive, Austin, TX 78712

    Email: pedretti@mit.edu

F. Associate or Co-investigator Contact Information

    Name: Leo W. Gordon

    Institution: UC Santa Barbara

    Address: UC Santa Barbara, Santa Barbara, California 93106

    Email: lwgordon@ucsb.edu

G. Associate or Co-investigator Contact Information

    Name: Nathaniel A. Lynd

    Institution: UT Austin

    Address: Main Building (MAI), 110 Inner Campus Drive, Austin, TX 78712

    Email: lynd@che.utexas.edu

H. Associate or Co-investigator Contact Information

    Name: Raphaële J. Clément

    Institution: UC Santa Barbara

    Address: UC Santa Barbara, Santa Barbara, California 93106

    Email: rclement@ucsb.edu

3. Date of data collection (single date, range, approximate date): 2022-2024

4. Geographic location of data collection: 34.41516955076635, -119.84146415350763

5. Information about funding sources that supported the collection of the data:

We gratefully acknowledge support from the Army Research Office (W911NF2310015). NMR characterization performed by LWG and RJC was supported by IRG-1 of the Materials Research Science and Engineering Center (MRSEC) at UC Santa Barbara: NSF DMR-2308708. We also made significant use of the facilities of the UC Santa Barbara MRSEC, which is a member of the Materials Research Facilities Network (www.mrfn.com). Some polymer synthesis was performed by BJP and NAL as supported as part of the Center for Materials for Water and Energy Systems (M-WET), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE-SC0019272.

METHODOLOGICAL INFORMATION

1. Description of methods used for collection/generation of data: See supporting information from published main text. https://doi.org/10.1021/acsmacrolett.4c00158

A summarized methodology is as follows: Polymerized were prepared via anionic ring-opening polymerization and subsequently functionalized with imidazole ligands. Characterization of polymer synthesis includes nuclear magnetic resonance spectroscopy and gel-permeation chromatography. Polymers were solvent-casted with Li and Ni salts. Salt-loaded polymer electrolytes were then characterized with oscillatory shear rheology, differential scanning calorimetry, electrochemical impedance spectroscopy, chronoamperometry, and pulsed field gradient nuclear magnetic resonance spectroscopy.

2. Methods for processing the data: See supporting information from published main text. https://doi.org/10.1021/acsmacrolett.4c00158

The raw data included in this upload was directly converted into manuscript figures using standard Python and Igor graphing software. In addition, MestReNova was used to graph 1H nuclear magnetic resonance spectroscopy.

3. Instrument- or software-specific information needed to interpret the data: N/A

4. Standards and calibration information, if appropriate: N/A

5. Environmental/experimental conditions: N/A

6. Describe any quality-assurance procedures performed on the data: See supporting information from published main text. https://doi.org/10.1021/acsmacrolett.4c00158

7. People involved with sample collection, processing, analysis and/or submission: James Bamford, Seamus Jones, Benjamin Pedretti, Leo Gordon

Files and variables

DATA & FILE OVERVIEW

1. File List: Files are organized into folders based on figure number from the corresponding manuscript: Capital letters = folder names, lower case letters = file names, 1. = list of column names.

A. TOC Figure

    a. TOC Figure_Li Conductivity.csv

        1\. r_Ni, Li Conductivity (S/cm), Li Conductivity Error (S/cm)

    b. TOC Figure_Shear Modulus.csv

        1\. r_Ni, Shear Modulus (Pa)

B. Figure 2

    a. Figure 2_Li Only.csv

        1\. frequency, storage modulus (pa), loss modulus (pa)

    b. Figure 2_Li Plus Ni.csv

        1\. frequency, storage modulus (pa), loss modulus (pa)

C. Figure 3

    a. Figure 3_AbsoluteTemp_Li Only.csv

        1\. 1000 / T (1/K), Conductivity (S/cm)

    b. Figure 3_AbsoluteTemp_Li Plus Ni.csv

        1\. 1000 / T (1/K), Conductivity (S/cm)

    c. Figure 3_NormalizedTemp_Li Only.csv

        1\. 1000 / (T - Tg + 50) (1/K), Conductivity (S/cm)

    d. Figure 3_NormalizedTemp_Li Plus Ni.csv

        1\. 1000 / (T - Tg + 50) (1/K), Conductivity (S/cm)

D. Figure 4

    a. Figure 4.csv

        1\. r_Ni, Li Inverse Haven Ratio

E. Figure 5

    a. Figure 5.csv

        1\. r_Ni, D_Li / D_TFSI

F. Figure 6

    a. Figure 6_a_Li Conductivity_Li Only.csv

        1\. r_Li, Li Conductivity (S/cm)

    b. Figure 6_a_Li Conductivity_Li Plus Ni.csv

        1\. r_Li, Li Conductivity (S/cm)

    c. Figure 6_a_Shear Modulus_Li Only.csv

        1\. r_Li, Shear Modulus (Pa)

    d. Figure 6_a_Shear Modulus_Li Plus Ni.csv

        1\. r_Li, Shear Modulus (Pa)

    e. Figure 6_b_Li Conductivity.csv

        1\. r_Ni, Li Conductivity (S/cm)

    f. Figure 6_b_Shear Modulus.csv

        1\. r_Ni, Shear Modulus (Pa)

G. Figures S1-3

    a. S1.csv

        1\. PPM, Counts

    b. S2.csv

        1\. PPM, Counts

    c. S3.csv

        1\. PPM, Counts

H. Figure S4

    a. S4.csv

        1\. Molecular Weight (g/mol), Counts

I. Figure S5

    a. S5_PAGE_Li_Ni.csv

        1\. Frequency (rad/s), Storage Modulus (Pa), Loss Modulus (Pa)

    b. S5_PIm_Li_Ni.csv

        1\. Frequency (rad/s), Storage Modulus (Pa), Loss Modulus (Pa)

    c. S5_PIm_Li.csv

        1\. Frequency (rad/s), Storage Modulus (Pa), Loss Modulus (Pa)

J. Figure S6

    a. S6_a_Li-0_Ni-0.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    b. S6_a_Li-0_Ni-8.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    c. S6_a_Li-4_Ni-0.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    d. S6_a_Li-4_Ni-8.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    e. S6_a_Li-8_Ni-0.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    f. S6_a_Li-8_Ni-8.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    g. S6_a_Li-12_Ni-0.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    h. S6_a_Li-12_Ni-8.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    i. S6_a_Li-16_Ni-0.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    j. S6_a_Li-16_Ni-8.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    k. S6_b_Li-16_Ni-0.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    l. S6_b_Li-16_Ni-2.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    m. S6_b_Li-16_Ni-4.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    n. S6_b_Li-16_Ni-6.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

    o. S6_b_Li-16_Ni-8.csv

        1\. Storage Modulus (Pa), Frequency (rad/s)

K. Figure S7

    a. S7_Glass-Relaxation_Li-16_Ni-X.csv

        1\. Glass Relaxation Time (s), rNi

    b. S7_Glass-Relaxation_Li-X_Ni-0.csv

        1\. Glass Relaxation Time (s), rNi

    c. S7_Glass-Relaxation_Li-X_Ni-8.csv

        1\. Glass Relaxation Time (s), rNi

    d. S7_Plateau-Modulus_Li-16_Ni-X.csv

        1\. Plateau Modulus (Pa), rNi

    e. S7_Plateau-Modulus_Li-X_Ni-0.csv

        1\. Plateau Modulus (Pa), rNi

    f. S7_Plateau-Modulus_Li-X_Ni-8.csv

        1\. Plateau Modulus (Pa), rNi

    g. S7_Terminal-Relaxation_Li-16_Ni-X.csv

        1\. Terminal Relaxation Time (s), rNi

    h. S7_Terminal-Relaxation_Li-X_Ni-0.csv

        1\. Terminal Relaxation Time (s), rNi

    i. S7_Terminal-Relaxation_Li-X_Ni-8.csv

        1\. Terminal Relaxation Time (s), rNi

L. Figure S8

    a. S8_Li-0_Ni-0.csv

        1\. Heat Flow (W/g), Temperature (C)

    b. S8_Li-0_Ni-8.csv

        1\. Heat Flow (W/g), Temperature (C)

    c. S8_Li-4_Ni-0.csv

        1\. Heat Flow (W/g), Temperature (C)

    d. S8_Li-4_Ni-8.csv

        1\. Heat Flow (W/g), Temperature (C)

    e. S8_Li-8_Ni-0.csv

        1\. Heat Flow (W/g), Temperature (C)

    f. S8_Li-8_Ni-8.csv

        1\. Heat Flow (W/g), Temperature (C)

    g. S8_Li-12_Ni-0.csv

        1\. Heat Flow (W/g), Temperature (C)

    h. S8_Li-12_Ni-8.csv

        1\. Heat Flow (W/g), Temperature (C)

    i. S8_Li-16_Ni-0.csv

        1\. Heat Flow (W/g), Temperature (C)

    j. S8_Li-16_Ni-2.csv

        1\. Heat Flow (W/g), Temperature (C)

    k. S8_Li-16_Ni-4.csv

        1\. Heat Flow (W/g), Temperature (C)

    l. S8_Li-16_Ni-6.csv

        1\. Heat Flow (W/g), Temperature (C)

    m. S8_Li-16_Ni-8.csv

        1\. Heat Flow (W/g), Temperature (C)

M. Figure S9

    a. S9.csv

        1\. rNi, Li T1 Relaxation Time (ms), F T1 Relaxation Time (ms), Li T2 Relaxation Time (ms), F T2 Relaxation Time (ms)

N. Figure S10

    a. S10.csv

        1\. rNi, Li Diffusion Coefficient (m2/s), F Diffusion Coefficient (m2/s)

O. Figure S11

    a. S11_a.csv

        1\. Gradient Strength (T/m), I/I0

    b. S11_b.csv

        1\. Gradient Strength (T/m), I/I0

    c. S11_c.csv

        1\. Gradient Strength (T/m), I/I0

    d. S11_d.csv

        1\. Gradient Strength (T/m), I/I0

    e. S11_e.csv

        1\. Gradient Strength (T/m), I/I0

    f. S11_f.csv

        1\. Gradient Strength (T/m), I/I0

    g. S11_g.csv

        1\. Gradient Strength (T/m), I/I0

    h. S11_h.csv

        1\. Gradient Strength (T/m), I/I0

P. Figure S12

    a. S12_Chronoamperometry.csv

        1\. Current (uA), Time (hr)

    b. S12_EIS_After-Polarization_Fit.csv

        1\. Negative Imaginary Impedance (kΩ), Real Impedance (kΩ)

    c. S12_EIS_After-Polarization.csv

        1\. Negative Imaginary Impedance (kΩ), Real Impedance (kΩ)

    d. S12_EIS_Before-Polarization_Fit.csv

        1\. Negative Imaginary Impedance (kΩ), Real Impedance (kΩ)

    e. S12_EIS_Before-Polarization.csv

        1\. Negative Imaginary Impedance (kΩ), Real Impedance (kΩ)

2. Relationship between files, if important: N/A

3. Additional related data collected that was not included in the current data package: N/A

4. Are there multiple versions of the dataset? no

Access information

SHARING/ACCESS INFORMATION

1. Licenses/restrictions placed on the data: N/A

2. Links to publications that cite or use the data: https://doi.org/10.1021/acsmacrolett.4c00158

3. Links to other publicly accessible locations of the data: N/A

4. Links/relationships to ancillary data sets: N/A

5. Was data derived from another source? no

A. If yes, list source(s): N/A

6. Recommended citation for this dataset: Bamford, James et al. (2024) Improved Mechanical Strength Without Sacrificing Li-ion Transport in Polymer Electrolytes, Dryad, Dataset, https://doi.org/10.5061/dryad.5x69p8dd5