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Title: Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1373206
DOE Contract Number:
AC02-76SF00515
Resource Type:
Journal Article
Resource Relation:
Journal Name: Nature Energy; Journal Volume: 2; Journal Issue: 5
Country of Publication:
United States
Language:
English

Citation Formats

Liu, Wei, Lee, Seok Woo, Lin, Dingchang, Shi, Feifei, Wang, Shuang, Sendek, Austin D., and Cui, Yi. Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires. United States: N. p., 2017. Web. doi:10.1038/nenergy.2017.35.
Liu, Wei, Lee, Seok Woo, Lin, Dingchang, Shi, Feifei, Wang, Shuang, Sendek, Austin D., & Cui, Yi. Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires. United States. doi:10.1038/nenergy.2017.35.
Liu, Wei, Lee, Seok Woo, Lin, Dingchang, Shi, Feifei, Wang, Shuang, Sendek, Austin D., and Cui, Yi. Mon . "Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires". United States. doi:10.1038/nenergy.2017.35.
@article{osti_1373206,
title = {Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires},
author = {Liu, Wei and Lee, Seok Woo and Lin, Dingchang and Shi, Feifei and Wang, Shuang and Sendek, Austin D. and Cui, Yi},
abstractNote = {},
doi = {10.1038/nenergy.2017.35},
journal = {Nature Energy},
number = 5,
volume = 2,
place = {United States},
year = {Mon Apr 03 00:00:00 EDT 2017},
month = {Mon Apr 03 00:00:00 EDT 2017}
}
  • Composite polymer electrolytes (CPEs) have been prepared by encapsulating electrolyte solutions of inorganic lithium salts dissolved in a plasticizer or mixture of plasticizers such as ethylene carbonate (EC), propylene carbonate (PC), {gamma}-butyrolactone (BL) and dimethyl carbonate (DMC), into porous polymer membranes. These polymer membranes are obtained from microemulsion polymerization of the microemulsion system of acrylonitrile, 4-vinylbenzenesulfonic acid lithium salt, ethylene glycol dimethacrylate (as cross-linker), {omega}-methoxy poly(ethyleneoxy){sub 40} undecyl-{alpha}-methacrylate (as surfactant), and water. These CPEs exhibit conductivities of 3.1 x 10{sup {minus}4} to 1.2 x 10{sup {minus}3} S cm{sup {minus}1} at room temperature. The lithium ion transference number, measured using amore » dc polarization method coupled with ac impedance spectroscopy, is found to be ca. 0.45. Cyclic voltammetry of the CPEs on stainless steel electrodes shows electrochemical stability windows extending up to 3.9, 4.0, and 4.4 V vs. Li{sup +}/Li for CPEs with 1 M LiSO{sub 3}CF{sub 3}/EC-PC (1:1 by volume), 1 M LiBF{sub 4}/BL and 1 M LiClO{sub 4}/EC-DMC (1:1 by volume), respectively. The impedance of the Li/CPE interface for the CPE with 1 M LiClO{sub 4}/EC-DMC under open circuit conditions is found to increase over storage time. Preliminary charge-discharge tests of prototype Li/CPE/LiMn{sub 2}O{sub 4} cells show an initial discharge capacity of ca. 118 mAh g{sup {minus}1} of LiMn{sub 2}O{sub 4} at a discharge current rate of 0.10 mA cm{sup {minus}2}, and promising cyclability.« less
  • Ionic conductivity measurements on LiAlSiO/sub 4/ glass and glass-ceramic showed these materials to be good lithium ion conducting solid electrolytes at high temperatures. This composition crystallizes in the ..beta..-eucryptite structure which is attractive for solid electrolyte applications because of its low thermal expansion. The glasses were prepared by quenching from the melt and were annealed to remove strain. The glass-ceramic (..beta..-eucryptite) samples were crystallized (aided by TiO/sub 2/ and ZrO/sub 2/ nucleating agents) by using a heat treatment determined through differential thermal analysis. The conductivity (sigma) was measured (to 650/sup 0/C) with a variety of techniques, including 2-terminal a.c., 3-terminalmore » guarded a.c., 4-terminal a.c., 2-terminal d.c., and a pulsed method. Vapor-deposited Cr contacts were used. Different sample geometries, contact geometries, and measurement circuitries were employed. All results are in excellent agreement, and the a-c techniques appear to be the most versatile and accurate of the methods examined. In these materials the conductivity is thermally activated (sigma = sigma/sub 0/e/sup -E/kT/) with typical values of sigma/sub 0/ = 1.9 x 10/sup 2/ (ohm-cm)/sup -1/ and E approximately 0.68 eV for the glasses, and sigma/sub 0/ = 2.1 x 10/sup 4/ (ohm-cm)/sup -1/ and E approximately 1.05 eV for the glass-ceramics. The TiO/sub 2/ and ZrO/sub 2/ nucleating agents (concentrations up to 2.8 mole percent) did not appear to influence the ionic conductivity. Data were also taken on a (..beta..-eucryptite) glass-ceramic with a composition near the ..beta..-eucryptite/..beta..-spodumene phase boundary. The ionic conductivity of this material is lower than that of the LiAlSiO/sub 4/ materials. Data are also provided on ..beta..-spodumene material. 8 figures, 35 references. (auth)« less
  • We prepared the b-axis-oriented polycrystalline Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} (NTGO) embedded in Ga{sub 2}O{sub 3}-doped Na{sub 2}Ti{sub 4}O{sub 9} matrix using the reactive diffusion technique. When the sandwich-type Ga{sub 2}TiO{sub 5}/NaGaO{sub 2}/Ga{sub 2}TiO{sub 5} diffusion couple was heated at 1323 K for 24 h, the NTGO polycrystal was readily formed in the presence of a liquid phase. The resulting polycrystalline material was characterized by X-ray diffractometry, electron microscopy and impedance spectroscopy. We mechanically processed the annealed diffusion couple and obtained the thin-plate electrolyte consisting mostly of the grain-aligned NTGO polycrystal. The ionic conductivity (σ) of the electrolyte along themore » common b-axis direction steadily increased from 1.3×10{sup −4} to 7.3×10{sup −3} S/cm as the temperature increased from 573 to 1073 K. There was a slope change at ca. 792 K for the Arrhenius plot of σ; the activation energies were 0.39 eV above this temperature and 0.57 eV below it. The NTGO showed the crystal structure (space group C2/m) with substantial positional disordering of one of the two Ga sites. The Na{sup +} ions occupied ca. 43% of the Wyckoff position 4i site, the deficiency of which would contribute to the relatively high ionic conductivity along the b-axis. The reactive diffusion could be widely applicable as the novel technique to the preparation of grain-aligned ceramics of multi-component systems. - Graphical abstract: We have prepared the b-axis-oriented Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} polycrystal embedded in Ga{sub 2}O{sub 3}-doped Na{sub 2}Ti{sub 4}O{sub 9} matrix by the heat treatment of sandwich-type diffusion couple of Ga{sub 2}TiO{sub 5}/NaGaO{sub 2}/Ga{sub 2}TiO{sub 5}. The resulting Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} electrolyte showed the ionic conductivity ranging from 1.3×10{sup −4} S/cm at 573 K to 7.3×10{sup −3} S/cm at 1073 K. - Highlights: • The b-axis-oriented polycrystalline Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} is successfully prepared. • Crystal structure of Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} is determined by single-crystal XRD. • The polycrystal shows relatively high Na{sup +} ion conductivity along the common b-axis. • Reactive diffusion is successfully used for the preparation of grain-aligned ceramics.« less
  • The ionic conductivity of a solid polymer electrolyte based on a lithium salt dissolved in a poly(ethylene oxide) (PEO) host was significantly improved with the use of plasticizing agents. Either a plasticizing salt, solvent, or combinations of both were incorporated into free-standing solution-cast films of (PEO){sub x}(LiCF{sub 3}SO{sub 3}). The greatest enhancement of conductivity was observed when a plasticizing salt (LiN[CF{sub 3}SO{sub 2}]{sub 2}) and solvent (diethyl phthalate) were combined, with the most notable improvement occurring below the melting temperature of PEO ({approx}66 C). Conductivity increased from 7.7 {times} 10{sup {minus}7} S/cm at 20 C to 4.6 {times} 10{sup {minus}5}more » S/cm with the addition of both plasticizers.« less