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: One-step fabrication of robust lithium ion battery separators by polymerization-induced phase separation
Conventional lithium ion battery separators are microporous polyolefin membranes that play a passive role in the electrochemical cell. Next generation separators should offer significant performance enhancements, while being fabricated through facile, low cost approaches with the ability to readily tune physicochemical properties. This study presents a single-step manufacturing technique based on UV-initiated polymerization-induced phase separation (PIPS), wherein microporous separators are fabricated from multifunctional monomers and ethylene carbonate (EC), which functions as both the pore-forming agent (porogen) and electrolyte component in the electrochemical cell. By controlling the ratio of the 1,4-butanediol diacrylate (BDDA) monomer to ethylene carbonate, monolithic microporous membranes are readily prepared with 25 μm thickness and pore sizes and porosities ranging from 6.8 to 22 nm and 15.4% to 38.5%, respectively. With 38.5% apparent porosity and an average pore size of 22 nm, the poly(1,4-butanediol diacrylate) (pBDDA) separator takes up 127% liquid electrolyte, resulting in an ionic conductivity of 1.98 mS cm −1 , which is greater than in conventional Celgard 2500. Lithium ion battery half cells consisting of LiNi 0.5 Mn 0.3 Co 0.2 O 2 cathodes and pBDDA separators were shown to undergo reversible charge/discharge cycling with an average discharge capacity of 142 mA h g −1 and a capacity retention of 98.4% over 100 cycles – comparable to cells using state-of-the-art separators. Moreover, similar discharge capacities were achieved in rate performance tests due to the high ionic conductivity and electrolyte uptake of the film. The pBDDA separators were shown to be thermally stable to 374 °C, lack low temperature thermal transitions that can compromise cell safety, and exhibit no thermal shrinkage up to 150 °C.  more » « less
Award ID(s):
1845805
PAR ID:
10403702
Author(s) / Creator(s):
;
Date Published:
Journal Name:
Journal of Materials Chemistry A
Volume:
10
Issue:
19
ISSN:
2050-7488
Page Range / eLocation ID:
10557 to 10568
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Suppressing Li dendrite growth has gained research interest due to the high theoretical capacity of Li metal anodes. Traditional Celgard membranes which are currently used in Li metal batteries fall short in achieving uniform Li flux at the electrode/electrolyte interface due to their inherent irregular pore sizes. Here, the use of an ultrathin (≈1.2 nm) carbon nanomembrane (CNM) which contains sub‐nanometer sized pores as an interlayer to regulate the mass transport of Li‐ions is demonstrated. Symmetrical cell analysis reveals that the cell with CNM interlayer cycles over 2x longer than the control experiment without the formation of Li dendrites. Further investigation on the Li plating morphology on Cu foil reveals highly dense deposits of Li metal using a standard carbonate electrolyte. A smoothed‐particle hydrodynamics simulation of the mass transport at the anode–electrolyte interface elucidates the effect of the CNM in promoting the formation of highly dense Li deposits and inhibiting the formation of dendrites. A lithium metal battery fabricated using the LiFePO4cathode exhibits a stable, flat voltage profile with low polarization for over 300 cycles indicating the effect of regulated mass transport. 
    more » « less
  2. Sodium metal batteries are an emerging technology that shows promise in terms of materials availability with respect to lithium batteries. Solid electrolytes are needed to tackle the safety issues related to sodium metal. In this work, a simple method to prepare a mechanically robust and efficient soft solid electrolyte for sodium batteries is demonstrated. A task-specific iongel electrolyte was prepared by combining in a simple process the excellent performance of sodium metal electrodes of an ionic liquid electrolyte and the mechanical properties of polymers. The iongel was synthesized by fast (<1 min) UV photopolymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of a saturated 42%mol solution of sodium bis(fluorosulfonyl)imide (NaFSI) in trimethyl iso-butyl phosphonium bis(fluorosulfonyl)imide (P111i4FSI). The resulting soft solid electrolytes showed high ionic conductivity at room temperature (≥10−3 S cm−1) and tunable storage modulus (104–107 Pa). Iongel with the best ionic conductivity and good mechanical properties (Iongel10) showed excellent battery performance: Na/iongel/NaFePO4 full cells delivered a high specific capacity of 140 mAh g−1 at 0.1 C and 120 mAh g−1 at 1 C with good capacity retention after 30 cycles. 
    more » « less
  3. 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
  4. The performance of the rechargeable Li metal battery anode is limited by the poor ionic conductivity and poor mechanical properties of its solid-electrolyte interphase (SEI) layer. To overcome this, a 3 : 1 v/v ethyl methyl carbonate (EMC) : fluoroethylene carbonate (FEC) containing 0.8 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 0.2 M lithium difluoro(oxalate)borate (LiDFOB) dual-salts with 0.05 M lithium hexafluorophosphate (LiPF 6 ) was tested to promote the formation of a multitude of SEI-beneficial species. The resulting SEI layer was rich in LiF, Li 2 CO 3 , oligomeric and glass borates, Li 3 N, and Li 2 S, which enhanced its role as a protective yet Li + conductive film, stabilizing the lithium metal anode and minimizing dead lithium build-up. With a stable SEI, a Li/Li[Ni 0.59 Co 0.2 Mn 0.2 Al 0.01 ]O 2 Li-metal battery (LMB) retains 75% of its 177 mA h g −1 specific discharge capacity for 500 hours at a coulombic efficiency of greater than 99.3% at the fast charge–discharge rate of 1.8 mA cm −2 . 
    more » « less
  5. In this study, the use of a closo-borate salt as an electrolyte for lithium-ion batteries (LIB) was evaluated in a series of solvent systems. The lithium closo-borate salts are a unique class of halogen-free salts that have the potential to offer some advantages over the halogenated salts currently employed in commercially available LIB due to their chemical and thermal stability. To evaluate this concept, three different solvent systems were prepared with a lithium closo-borate salt to make a liquid electrolyte (propylene carbonate, ethylene carbonate:dimethyl carbonate, and 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide). The closo-borate containing electrolytes were then compared by utilizing them with three different electroactive electrode materials. Their cycle stability and performance at various charge/discharge rates was also investigated. Based on the symmetrical cell and galvanostaic cycling studies it was determined that the carbonate based liquid electrolytes performed better than the ionic liquid electrolyte. This work demonstrates that halogen free closo-borate salts are interesting candidates and worthy of further investigation as lithium salts for LIB. 
    more » « less