skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: The Soret effect in dry polymer electrolyte
The Soret effect results in a concentration gradient when a mixture is exposed to a temperature gradient. It is a balance between diffusion of mass driven by the temperature gradient (thermal diffusion) and mass diffusion acting to remove the concentration gradient. Thus, the Soret effect is measured at steady state. In this work, the Soret effect was studied in a thermogalvanic cell with lithium metal electrodes and a dry polymer electrolyte composed of poly(ethylene oxide) and lithium bis-trifluoromethanesulfonylimide (LiTFSI). The concentration gradient was determined by measuring the voltage of the thermogalvanic cell. This was examined at several different temperature gradients and with four different salt concentrations. The Soret coefficient was found to be similar to that observed in small-molecule mixtures and electrolytes and significantly less than polymeric systems. An explanation for this unexpected result is proffered. The Soret coefficient was found to be concentration dependent, which requires further investigation. Finally, it was demonstrated that the thermogalvanic cells used to measure the Soret coefficient can also be used to generate power. Thus, polymer electrolytes are potentially of interest for waste heat recovery, and thermal diffusion might be used to improve battery efficiency.  more » « less
Award ID(s):
1751450 1804871
PAR ID:
10283809
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Molecular Systems Design & Engineering
Volume:
5
Issue:
4
ISSN:
2058-9689
Page Range / eLocation ID:
856 to 863
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. The design of safe and high-performance, nanostructured, block polymer (BP) electrolytes for lithium-ion batteries requires a thorough understanding of the key parameters that govern local structure and dynamics. Yet, the interfaces between microphase-separated domains can introduce complexities in this local behavior that can be challenging to quantify. Herein, the local polymer, cation (Li+), and anion dynamics were described in salt-doped polystyrene-block-poly(oligo-oxyethylene methyl ether methacrylate) (PS-b-POEM) through a quantitative framework that considered the effects of polymer architecture, segmental mixing, chain stretching, and confinement on polymer mobility and ion transport. This framework was validated through nuclear magnetic resonance (NMR) spectroscopy measurements on solid (dry) polymer electrolyte samples. Notably, a mobility transition temperature (Tmobility) was identified through NMR spectroscopy that captured the local dynamics more accurately than the thermal glass transition temperature. Additionally, the approach quantitatively described the mobility gradient across a domain when segmental mixing effects were combined with chain stretching and confinement information, especially at higher segregation strengths – facilitating the assessment of local ion diffusion and conductivity. Spatially averaged local ion diffusion predictions quantitatively matched NMR-measured ion diffusivities in the BP samples, while spatially summed ionic conductivity predictions across a domain qualitatively captured trends in the measured ionic conductivities. 
    more » « less
  2. Solid polymer electrolytes offer potential improvements to lithium ion batteries that include extending their operating temperature range and improving the safe use of the batteries by inhibiting lithium dendrite formation. Because solid polymer electrolytes replace traditional liquid electrolytes as the lithium ion transport medium and also act as the electrode separator, these materials must offer good ionic conductivity along with providing good interfacial contact with the electrode material. This work presents the synthesis and characterization of polymer blends comprised poly(ethylene oxide) and phosphonium ionenes. Ionenes are a class of polycation that includes positive charges within the polymer backbone. Because the positive charge is a part of the polymer chain, the spacing and distribution of these charges have a significant impact on the properties of ionenes. This research focuses on determining the role of charge spacing and distribution of charges along the backbone of phosphonium ionenes on their ability to transport lithium ions. To accomplish this, phosphonium ionenes are blended with low molecular weight poly(ethylene oxide) (e.g. less than 3,000 g/mol) at mass ratios of 20:1, 10:1, and 5:1. The resulting blended solid polymer electrolyte membranes are evaluated for their thermal, mechanical and electrochemical properties along with their charge/discharge performance in coin cell batteries. The dependence of phosphonium ionene structure as well as the composition of SPE blends will be presented. 
    more » « less
  3. Abstract A thorough understanding of electrolyte transport properties is crucial in the development of alternative battery technology. As a key parameter, the diffusion coefficient offers important insights into the behavior of electrolytes, especially for fast charge of high-energy batteries. Existing methods of measurement are often limited by redox species or offer questionable accuracy due to side reactions and/or disruption of the diffusion profile. This work provides a novel optical method for measuring diffusion coefficients of liquid-phase concentrated battery electrolytes without electrochemical reactions. The method relies on the deflection of a refractive laser beam passing through an electrolyte of a minor concentration gradient in a triangular diffusion column. The diffusion coefficient, D, for a range of zinc sulfate electrolytes was successfully extracted by correlating the position of the laser beam to its concentration. Several other physicochemical properties of the same electrolytes are studied to correlate to the concentration-dependent diffusion coefficients, including viscosity, conductivity, and microstructure analysis based on vibrational spectroscopy (infrared and Raman). Also included is the future application of the triangular column for in situ electrochemical measurements. 
    more » « less
  4. In this study, the amphiphilic salt lithium trifluoromethanesulfonylimide octadecane (C18LiTFSI) was used as a basis to investigate the effects of anion density and cation coordination sites within blended electrolytes with strong ionic aggregation. C18LiTFSI was previously reported as a single-component, ion-condensed electrolyte with a wide layered liquid crystalline phase regime. Three additive molecules with varyingly sized polar sulfonyl groups attached to an octodecane-tail were synthesized and mixed with C18LiTFSI. The thermal properties, morphology, and ionic conductivity of the blended electrolytes were characterized. It was found that the blended electrolytes exhibited layered liquid crystalline morphology over a narrower temperature range than the pure salt, and the ionic conductivity of the blended liquid crystalline electrolytes were generally lower than that of the pure salt. Surprising, the additives were found to have the greatest effect on the bulk ionic conductivity of the semicrystalline phase of the electrolytes. Addition of minor fractions of methylsulfonyloctadecane to C18LiTFSI resulted in increases in conductivity of over two orders of magnitude at room temperature, while addition of ethylsulfonyloctadecane or isopropylsulfonyloctadecane with the larger head group resulted in decreased ionic conductivity over the entire composition space and temperature range investigated. 
    more » « less
  5. All-solid-state lithium ion batteries replace the traditional liquid electrolyte with a conductive solid polymer electrolyte. Replacing the liquid electrolyte in batteries has the potential to improve safe use of batteries without the need for hermetic sealing, extending the operating temperature range, and extending the lifetime of the battery. However, solid polymer electrolytes often have non-competitive conductivity compared to liquid electrolytes. Improving the conductivity of solid polymer electrolytes based on an understanding of structure-property relationships is not yet well understood, but it is believed to depend heavily on the localized segmental motion of polymer chains. This work attempts to describe the role of polymer segmental motion on lithium ion transport through the synthesis and characterization of phosphonium ionenes that include poly(ethylene oxide) “soft” segments. Synthetically, these segmented polymers offer an opportunity to systematically control the segmental motion of polymer chains (i.e. glass transition temperature) through control of PEO incorporation. Prepared by step-growth polymerization, these segmented phosphonium ionenes achieve molecular weights up to 40,000 g/mol. Also, the degradation and glass transition temperatures are dependent on the percent incorporation of PEO as determined by thermogravimetric analysis and differential scanning calorimetry, respectively. The ability to influence the physical properties of this unique class of polyelectrolyte provides a unique opportunity to systematically probe the impact of glass transition temperature on the ion transport properties of solid polymer electrolytes in lithium ion batteries. Our initial results from electrochemical impedance as well as the charge/discharge performance of these novel solid polymer electrolytes in coin cell battery assemblies will also be presented. 
    more » « less