DOI: 10.5061/dryad.m37pvmdcg
title: Converting a metal-coordinating polymer to a polymerized ionic liquid improves Li+ transport

description: Solid polymer electrolytes (SPEs) with mechanical strength and reduced
 flammability may also enable next-generation Li+ batteries with higher
 energy densities. However, conventional SPEs have fundamental limitations
 in terms of Li+ conductivity. While an imidazole functionalized polymer
 (PMS-Im) has been previously shown to have ionic conductivity related to
 the imidazole-Li+ coordination, herein we demonstrate that quaternization
 of this polymer to form an analogous imidazolium functionalized polymer
 (PMS-Im+) more efficiently solvates lithium salts and plasticizes the
 polymer. In addition, inverse Haven ratios as high as 10 indicate
 positively correlated Li+ transport, possibly due to percolation of
 nanochannels that significantly improve battery-relevant conductivity.
 From these combined effects, Li+ conductivity in PMS-Im+ (2.1*10-5 S/cm)
 is over an order of magnitude greater than in PMS-Im at 90 °C (1.6*10-6
 S/cm).
description: See supporting information from published main text.
 https://doi.org/10.1021/acsmacrolett.4c00704 In short, polymers were
 synthesized via anionic polymerization and subsequently functionalized
 through multiple steps. Polymers were then blended with Li salts and
 characterized via thermal, electrochemical, and spectroscopic
 methods.
description: # Converting a metal-coordinating polymer to a polymerized ionic liquid
 improves Li+ transport
 [https://doi.org/10.5061/dryad.m37pvmdcg](https://doi.org/10.5061/dryad.m37pvmdcg) ## Description of the data and file structure See supporting information from published main text. [https://doi.org/10.1021/acsmacrolett.4c00704](https://doi.org/10.1021/acsmacrolett.4c00704) In short, polymers were synthesized via anionic polymerization and subsequently functionalized through multiple steps. Polymers were then blended with Li salts and characterized via thermal, electrochemical, and spectroscopic methods. ### Files and variables #### File: RawData.zip **Description:** Files are organized into folders based on figure number from the corresponding manuscript: A. B. C... = folder names, a. b. c... = file names within folder, 1. 2. 3... = column names within file. The file list is followed by a list of variable names and descriptions. A. Figure 2 ``` a. Figure 2a.csv 1\. PMS-Im r03 1000/T 2\. PMS-Im r03 σEIS,Li (S/cm) 3\. PMS-Im r03 σEIS,Li (S/cm) error 4\. PMS-Im r10 1000/T 5\. PMS-Im r10 σEIS,Li (S/cm) 6\. PMS-Im r10 σEIS,Li (S/cm) error 7\. PMS-Im r30 1000/T 8\. PMS-Im r30 σEIS,Li (S/cm) 9\. PMS-Im r30 σEIS,Li (S/cm) error 10\. PMS-Im+ r03 1000/T 11\. PMS-Im+ r03 σEIS,Li (S/cm) 12\. PMS-Im+ r03 σEIS,Li (S/cm) error 13\. PMS-Im+ r10 1000/T 14\. PMS-Im+ r10 σEIS,Li (S/cm) 15\. PMS-Im+ r10 σEIS,Li (S/cm) error 16\. PMS-Im+ r30 1000/T 17\. PMS-Im+ r30 σEIS,Li (S/cm) 18\. PMS-Im+ r30 σEIS,Li (S/cm) error b. Figure 2b.csv 1\. PMS-Im r03 1000/(T-Tg+50) 2\. PMS-Im r03 σEIS,Li (S/cm) 3\. PMS-Im r03 σEIS,Li (S/cm) error 4\. PMS-Im r10 1000/(T-Tg+50) 5\. PMS-Im r10 σEIS,Li (S/cm) 6\. PMS-Im r10 σEIS,Li (S/cm) error 7\. PMS-Im r30 1000/(T-Tg+50) 8\. PMS-Im r30 σEIS,Li (S/cm) 9\. PMS-Im r30 σEIS,Li (S/cm) error 10\. PMS-Im+ r03 1000/(T-Tg+50) 11\. PMS-Im+ r03 σEIS,Li (S/cm) 12\. PMS-Im+ r03 σEIS,Li (S/cm) error 13\. PMS-Im+ r10 1000/(T-Tg+50) 14\. PMS-Im+ r10 σEIS,Li (S/cm) 15\. PMS-Im+ r10 σEIS,Li (S/cm) error 16\. PMS-Im+ r30 1000/(T-Tg+50) 17\. PMS-Im+ r30 σEIS,Li (S/cm) 18\. PMS-Im+ r30 σEIS,Li (S/cm) error ``` B. SI Figure 1 ``` a. SI Figure 1.csv 1\. PPM 2\. Counts ``` C. SI Figure 10 ``` a. SI Figure 10.csv 1\. I 2\. t ``` D. SI Figure 11 ``` a. SI Figure 11a.csv 1\. Gradient Strength (T/m) 2\. Normalized Intensity b. SI Figure 11b.csv 1\. Gradient Strength (T/m) 2\. Normalized Intensity c. SI Figure 11c.csv 1\. Gradient Strength (T/m) 2\. Normalized Intensity d. SI Figure 11d.csv 1\. Gradient Strength (T/m) 2\. Normalized Intensity ``` E. SI Figure 12 ``` a. SI Figure 12a.csv 1\. Gradient Strength (T/m) 2\. Normalized Intensity b. SI Figure 12b.csv 1\. Gradient Strength (T/m) 2\. Normalized Intensity c. SI Figure 12c.csv 1\. Gradient Strength (T/m) 2\. Normalized Intensity d. SI Figure 12d.csv 1\. Gradient Strength (T/m) 2\. Normalized Intensity ``` F. SI Figure 2 ``` a. SI Figure 2.csv 1\. Mn 2\. Counts ``` G. SI Figure 3 ``` a. SI Figure 3.csv 1\. PPM 2\. Counts ``` H. SI Figure 4 ``` a. SI Figure 4.csv 1\. PPM 2\. Counts ``` I. SI Figure 5 ``` a. SI Figure 5.csv 1\. PPM 2\. Counts ``` J. SI Figure 6 ``` a. SI Figure 6.csv 1\. PPM 2\. LiTFSI Counts 3\. PMS-Im+ Counts ``` K. SI Figure 7 ``` a. SI Figure 7.csv 1\. PMS-Im r0 Temperature (C) 2\. PMS-Im r0 Heat Flow 3\. PMS-Im r03 Temperature (C) 4\. PMS-Im r03 Heat Flow 5\. PMS-Im r10 Temperature (C) 6\. PMS-Im r10 Heat Flow 7\. PMS-Im r30 Temperature (C) 8\. PMS-Im r30 Heat Flow 9\. PMS-Im+ r0 Temperature (C) 10\. PMS-Im+ r0 Heat Flow 11\. PMS-Im+ r03 Temperature (C) 12\. PMS-Im+ r03 Heat Flow 13\. PMS-Im+ r10 Temperature (C) 14\. PMS-Im+ r10 Heat Flow 15\. PMS-Im+ r30 Temperature (C) 16\. PMS-Im+ r30 Heat Flow ``` L. SI Figure 8 ``` a. SI Figure 8 Fits.csv 1\. 30 C Real Impedance (Ohms) 2\. 30 C Negative Imaginary Impedance (Ohms) 3\. 40 C Real Impedance (Ohms) 4\. 40 C Negative Imaginary Impedance (Ohms) 5\. 50 C Real Impedance (Ohms) 6\. 50 C Negative Imaginary Impedance (Ohms) 7\. 60 C Real Impedance (Ohms) 8\. 60 C Negative Imaginary Impedance (Ohms) 9\. 70 C Real Impedance (Ohms) 10\. 70 C Negative Imaginary Impedance (Ohms) 11\. 80 C Real Impedance (Ohms) 12\. 80 C Negative Imaginary Impedance (Ohms) 13\. 90 C Real Impedance (Ohms) 14\. 90 C Negative Imaginary Impedance (Ohms) 15\. 100 C Real Impedance (Ohms) 16\. 100 C Negative Imaginary Impedance (Ohms) 17\. 110 C Real Impedance (Ohms) 18\. 110 C Negative Imaginary Impedance (Ohms) 19\. 120 C Real Impedance (Ohms) 20\. 120 C Negative Imaginary Impedance (Ohms) b. SI Figure 8 Measured.csv 1\. 30 C Real Impedance (Ohms) 2\. 30 C Negative Imaginary Impedance (Ohms) 3\. 40 C Real Impedance (Ohms) 4\. 40 C Negative Imaginary Impedance (Ohms) 5\. 50 C Real Impedance (Ohms) 6\. 50 C Negative Imaginary Impedance (Ohms) 7\. 60 C Real Impedance (Ohms) 8\. 60 C Negative Imaginary Impedance (Ohms) 9\. 70 C Real Impedance (Ohms) 10\. 70 C Negative Imaginary Impedance (Ohms) 11\. 80 C Real Impedance (Ohms) 12\. 80 C Negative Imaginary Impedance (Ohms) 13\. 90 C Real Impedance (Ohms) 14\. 90 C Negative Imaginary Impedance (Ohms) 15\. 100 C Real Impedance (Ohms) 16\. 100 C Negative Imaginary Impedance (Ohms) 17\. 110 C Real Impedance (Ohms) 18\. 110 C Negative Imaginary Impedance (Ohms) 19\. 120 C Real Impedance (Ohms) 20\. 120 C Negative Imaginary Impedance (Ohms) ``` M. SI Figure 9 ``` a. SI Figure 9.csv 1\. Initial Measured Real Impedance (Ohms) 2\. Initial Measured Negative Imaginary Impedance (Ohms) 3\. Initial Fitted Real Impedance (Ohms) 4\. Initial Fitted Negative Imaginary Impedance (Ohms) 5\. Polarized Measured Real Impedance (Ohms) 6\. Polarized Measured Negative Imaginary Impedance (Ohms) 7\. Polarized Fitted Real Impedance (Ohms) 8\. Polarized Fitted Negative Imaginary Impedance (Ohms) ``` N. SI Table 1 ``` a. SI Table 1.csv 1\. Polymer 2\. r 3\. Ri, total (Ohms) 4\. Ri, interfacial (Ohms) 5\. Rss, interfacial (Ohms) 6\. Iss (A) 7\. Ii (A) 8\. p+ ``` O. SI Table 2 ``` a. SI Table 2.csv 1\. Polymer 2\. DLi @ T=80 °C (10^–13 m^2 s^–1) 3\. DF @ T=80 °C (10^–13 m^2 s^–1) 4\. DLi @ T-Tg=120 °C (10^–13 m^2 s^–1) 5\. DF @ T-Tg=120 °C (10^–13 m^2 s^–1) ``` P. SI Table 3 ``` a. SI Table 3.csv 1\. Polymer 2\. D_Li (10^–13 m^2 s^–1) 3\. D_TFSI (10^–13 m^2 s^–1) 4\. c_Li (10^-4 mol/cm^3) 5\. c_TFSI (10^-4 mol/cm^3) 6\. σ_NE (10^-6 S/cm) 7\. σ_EIS (10^-6 S/cm) 8\. σ_NE,Li (10^-6 S/cm) 9\. σ_EIS,Li (10^-6 S/cm) 10\. H^-1 11\. H^-1_Li ``` Q. Table 1 ``` a. Table 1.csv 1\. Polymer 2\. r 3\. Tg (C) 4\. σEIS (10^-6 S/cm) 5\. σEIS (10^-6 S/cm) error 6\. ρLi 7\. σEIS, Li (10^-6 S/cm) 8\. σEIS, Li (10^-6 S/cm) error ``` R. Table 2 ``` a. Table 2.csv 1\. Polymer 2\. DLi (10^-13 m^2/s) 3\. t+ 4\. H^-1 5\. H^-1 error 6\. H^-1_Li 7\. H^-1_Li error ``` List of variable names and units, in order of appearance in the File List: a. PMS-Im rXX: designates a variable as pertaining to poly(methyl siloxane imidazole) samples loaded with LiTFSI salt at an r ratio of r = 0.XX, where r is the molar ratio of Li to monomer units b. PMS-Im+ rXX: designates a variable as pertaining to poly(methyl siloxane imidazolium) samples loaded with LiTFSI salt at an r ratio of r = 0.XX, where r is the molar ratio of Li to monomer units c. T: temperature, in Kelvin unless specified otherwise d. σEIS,Li: Li conductivity, as measured via electrochemical impedance spectroscopy (EIS), in S/cm unless specified otherwise e. PPM: chemical shift value for nuclear magnetic resonance (NMR) spectroscopy, in parts per million g. I: current, in mA h. t: time, in s i. Mn: molecular weight, in kg/mol j. Ri: initial resistance before polarization during a Bruce-Vincent measurement, in ohms k. Rss: steady state resistance after polarization during a Bruce-Vincent measurement, in ohms l. Iss: steady state current, in amps m. p+: limiting current fraction (also designated as pLi) n. D_x: Self-diffusion coefficient of species x, in m^2/s unless specified otherwise o. c_x: concentration of species x, in 10^-4 mol/cm^3 p. σ_NE: conductivity, as derived by the Nernst-Einstein (NE) equation, in S/cm unless specified otherwise q. σEIS: conductivity, as measured via electrochemical impedance spectroscopy (EIS), in S/cm unless specified otherwise r. σ_NE,Li: Li conductivity, as derived by the Nernst-Einstein (NE) equation, in S/cm unless specified otherwise s. H^-1: inverse Haven ratio t. H^-1_Li: Li inverse Haven ratio u. Tg: glass transition temperature, in Celsius v. t+: transport number ## Access information Other publicly accessible locations of the data: N/A Data was derived from the following sources: N/A