skip to main content


Title: Shape Persistent, Highly Conductive Ionogels from Ionic Liquids Reinforced with Cellulose Nanocrystal Network
Abstract

Shape‐persistent, conductive ionogels where both mechanical strength and ionic conductivity are enhanced are developed using multiphase materials composed of cellulose nanocrystals and hyperbranched polymeric ionic liquids (PILs) as a mechanically strong supporting network matrix for ionic liquids with an interrupted ion‐conducting pathway. The integration of needlelike nanocrystals and PIL promotes the formation of multiple hydrogen bonding and electrostatic ionic interaction capacitance, resulting in the formation of interconnected networks capable of confining a high amount of ionic liquid (≈95 wt%) without losing its self‐sustained shape. The resulting nanoporous and robust ionogels possess outstanding mechanical strength with a high compressive elastic modulus (≈5.6 MPa), comparable to that of tough, rubbery materials. Surprisingly, these rigid materials preserve the high ionic conductivity of original ionic liquids (≈7.8 mS cm−1), which are distributed within and supported by the nanocrystal network‐like rigid frame. On the one hand, such stable materials possess superior ionic conductivities in comparison to traditional solid electrolytes; on the other hand, the high compression resistance and shape‐persistence allow for easy handling in comparison to traditional fluidic electrolytes. The synergistic enhancement in ion transport and solid‐like mechanical properties afforded by these ionogel materials make them intriguing candidates for sustainable electrodeless energy storage and harvesting matrices.

 
more » « less
Award ID(s):
2001968
NSF-PAR ID:
10449713
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Functional Materials
Volume:
31
Issue:
38
ISSN:
1616-301X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Dusastre, Vincent (Ed.)
    A critical challenge for next-generation lithium-based batteries lies in development of electrolytes that enable thermal safety along with use of high-energy-density electrodes. We describe molecular ionic composite (MIC) electrolytes based on an aligned liquid crystalline polymer combined with ionic liquids and concentrated Li salt. This high strength (200 MPa) and non-flammable solid electrolyte possesses outstanding Li+ conductivity (1 mS·cm-1 at 25 °C) and electrochemical stability (5.6 V vs Li|Li+) while suppressing dendrite growth and exhibiting low interfacial resistance (32 Ω·cm2) and overpotentials (≤ 120 mV @ 1 mA·cm-2) during Li symmetric cell cycling. A heterogeneous salt doping process modifies a locally ordered polymer-ion assembly to incorporate an inter-grain network filled with defective LiFSI & LiBF4 nanocrystals, strongly enhancing Li+ conduction. This modular material fabrication platform shows promise for safe and high-energy-density energy storage and conversion applications, incorporating the fast transport of ceramic-like conductors with the superior flexibility of polymer electrolytes. 
    more » « less
  2. Abstract

    Ionogel electrolytes based on ionic liquids and gelling matrices offer several advantages for solid‐state lithium‐ion batteries, including nonflammability, wide processing compatibility, and favorable electrochemical and thermal properties. However, the absence of ionic liquids that are concurrently stable at low and high potentials constrains the electrochemical windows of ionogel electrolytes and thus their high‐energy‐density applications. Here, ionogel electrolytes with a layered heterostructure are introduced, combining high‐potential (anodic stability: >5 V vs Li/Li+) and low‐potential (cathodic stability: <0 V vs Li/Li+) imidazolium ionic liquids in a hexagonal boron nitride nanoplatelet matrix. These layered heterostructure ionogel electrolytes lead to extended electrochemical windows, while preserving high ionic conductivity (>1 mS cm−1at room temperature). Using the layered heterostructure ionogel electrolytes, full‐cell solid‐state lithium‐ion batteries with a nickel manganese cobalt oxide cathode and a graphite anode are demonstrated, exhibiting voltages that are unachievable with either the high‐potential or low‐potential ionic liquid alone. Compared to ionogel electrolytes based on mixed ionic liquids, the layered heterostructure ionogel electrolytes enable higher stability operation of full‐cell lithium‐ion batteries, resulting in significantly enhanced cycling performance.

     
    more » « less
  3. Abstract

    Chloroaluminate ionic liquids are commonly used electrolytes in rechargeable aluminum batteries due to their ability to reversibly electrodeposit aluminum at room temperature. Progress in aluminum batteries is currently hindered by the limited electrochemical stability, corrosivity, and moisture sensitivity of these ionic liquids. Here, a solid polymer electrolyte based on 1‐ethyl‐3‐methylimidazolium chloride‐aluminum chloride, polyethylene oxide, and fumed silica is developed, exhibiting increased electrochemical stability over the ionic liquid while maintaining a high ionic conductivity of ≈13 mS cm−1. In aluminum–graphite cells, the solid polymer electrolytes enable charging to 2.8 V, achieving a maximum specific capacity of 194 mA h g−1at 66 mA g−1. Long‐term cycling at 2.7 V showed a reversible capacity of 123 mA h g−1at 360 mA g−1and 98.4% coulombic efficiency after 1000 cycles. Solid‐state nuclear magnetic resonance spectroscopy measurements reveal the formation of five‐coordinate aluminum species that crosslink the polymer network to enable a high ionic liquid loading in the solid electrolyte. This study provides new insights into the molecular‐level design and understanding of polymer electrolytes for high‐capacity aluminum batteries with extended potential limits.

     
    more » « less
  4. Abstract

    A class of organic‐inorganic hybrid electrolyte with ion pair integrated network (X‐POSS‐IL‐LiTFSI) has been prepared by crosslinking of oligomeric octasilsesquioxanes grafted with imidazolium‐based ionic liquids for solid state lithium ion battery applications. X‐POSS‐IL‐LiTFSI is thermally stable and highly amorphous, and shows high ionic conductivities and excellent electrochemical stability. With further immobilization of a small fraction of ionic liquid, the ionic conductivity of X‐POSS‐IL‐LiTFSI has been significantly improved, e. g. 1.4×10−4 S/cm at ambinet temperature, to the level required by the practical battery applications, while maintaining the demensional integity. The coin cells of lithium batteries with the plasticized X‐POSS‐IL‐LiTFSI electrolytes exhibit high specific capacities at both ambient and elevated temperatures.

     
    more » « less
  5. Molecular ionic composites (MICs) are a new class of solid electrolytes that combine ionic liquids (ILs) and a rigid-rod double helical polyelectrolyte, poly(2,2′-disulfonyl-4,4′benzidine terephthalamide) (PBDT). In this study, we focus on the mechanical, dielectric, and ion diffusive dynamics of MICs with a fixed PBDT weight percent (10 wt%) and varying IL chemistry and molecular volume ( V m ). All six MICs produce tensile moduli in the range of 50–500 MPa at 30 °C, up to 60× higher than the shear moduli of the same MICs. The high range of moduli and tensile to shear modulus ratio emphasizes that the distribution of PBDT chains and the strong ionic interactions between IL ions and PBDT chains dictate the modulus and the mechanical strength in MICs. Additionally, these MICs exhibit high ionic conductivities ranging from 1–6 mS cm −1 at 30 °C, consistent with the measured diffusion coefficients of the IL ions. The tunability of the extraordinary mechanical properties and high ionic conductivities of MIC electrolytes greatly inspire their use in advanced electrochemical devices. 
    more » « less