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   
                    
                            
                            Printable hexagonal boron nitride ionogels
                        
                    
    
            Due to its excellent chemical/thermal stability and mechanical robustness, hexagonal boron nitride (hBN) is a promising solid matrix material for ionogels. While bulk hBN ionogels have been employed in macroscopic applications such as lithium-ion batteries, hBN ionogel inks that are compatible with high-resolution printing have not yet been realized. Here, we describe aerosol jet-printable ionogels using exfoliated hBN nanoplatelets as the solid matrix. The hBN nanoplatelets are produced from bulk hBN powders by liquid-phase exfoliation, allowing printable hBN ionogel inks to be formulated following the addition of an imidazolium ionic liquid and ethyl lactate. The resulting inks are reliably printed with variable patterns and controllable thicknesses by aerosol jet printing, resulting in hBN ionogels that possess high room-temperature ionic conductivities and storage moduli of >3 mS cm −1 and >1 MPa, respectively. By integrating the hBN ionogel with printed semiconductors and electrical contacts, fully-printed thin-film transistors with operating voltages below 1 V are demonstrated on polyimide films. These devices exhibit desirable electrical performance and robust mechanical tolerance against repeated bending cycles, thus confirming the suitability of hBN ionogels for printed and flexible electronics. 
        more » 
        « less   
        
    
                            - Award ID(s):
- 2039268
- PAR ID:
- 10379053
- Date Published:
- Journal Name:
- Faraday Discussions
- Volume:
- 227
- ISSN:
- 1359-6640
- Page Range / eLocation ID:
- 92 to 104
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
- 
            
- 
            Abstract The proliferation and miniaturization of portable electronics require energy‐storage devices that are simultaneously compact, flexible, and amenable to scalable manufacturing. In this work, mechanically flexible micro‐supercapacitor arrays are demonstrated via sequential high‐speed screen printing of conductive graphene electrodes and a high‐temperature hexagonal boron nitride (hBN) ionogel electrolyte. By combining the superlative dielectric properties of 2D hBN with the high ionic conductivity of ionic liquids, the resulting hBN ionogel electrolyte enables micro‐supercapacitors with exceptional areal capacitances that approach 1 mF cm−2. Unlike incumbent polymer‐based electrolytes, the high‐temperature stability of the hBN ionogel electrolyte implies that the printed micro‐supercapacitors can be operated at unprecedentedly high temperatures up to 180 °C. These elevated operating temperatures result in increased power densities that make these printed micro‐supercapacitors particularly promising for applications in harsh environments such as underground exploration, aviation, and electric vehicles. The combination of enhanced functionality in extreme conditions and high‐speed production via scalable additive manufacturing significantly broadens the technological phase space for on‐chip energy storage.more » « less
- 
            Printable feedstocks that can produce lightweight, robust, and ductile structures with tunable and switchable conductivity are of considerable interest for numerous application spaces. Combining the specific properties of commodity thermoplastics with the unique electrical and redox properties of conducting polymers (CPs) presents new opportunities for the field of printed (bio)electronics. Here, we report on the direct ink write (DIW) printing of ink formulations based on polyaniline-dinonylnaphthalene sulfonic acid (PANI-DNNSA), which has been synthesized in bulk quantities (∼400 g). DNNSA imparts solubility to PANI up to 50 mg mL −1 , which allows the use of various additives to tune the rheological behavior of the inks without significantly compromising the electrical properties of the printed structures, which reach conductivities in the range of <10 −7 –10 0 S cm −1 as a function of ink formulation and post treatment used. Fumed silica (FS) and ultra-high molecular weight polystyrene (UHMW-PS) additives are leveraged to endow printability and shape retention to inks, as well as to compare the use of traditional rheological modifiers with commodity thermoplastics on CP feedstocks for tailored DIW printing. We show that the incorporation of UHMW-PS into these ink formulations is critical for obtaining high crack resistance in printed structures. This work serves as a guide for future ink designs of CPs with commodity thermoplastics and their subsequent DIW printing to yield conductive architectures and devices for various applications.more » « less
- 
            When a hydrogel simply won’t cut it – either because it dries out too quickly, or it does not tolerate more than roughly one volt when applied in an electrochemical device – where is the savvy materials researcher to turn? This is where two important classes of nonaqueous gel counterparts, known as ionogels and eutectogels, can truly shine. Replacing the aqueous liquid phase of a hydrogel with either an ionic liquid (IL) or a deep eutectic solvent (DES) allows one to realize an array of versatile gel electrolyte materials that offer outstanding nonvolatility, wider windows of electrochemical stability, reasonably high ionic conductivity, and nearly unlimited chemical design possibilities. In addition to choosing a specific IL or DES, there are a myriad of options when it comes to constructing a solid, three-dimensional, volume-spanning network (or scaffold) that will support the nonaqueous liquid phase of an ionogel or eutectogel. In this focused review, several recent approaches to forming these gels using noncovalent scaffold assembly and cross-linking are examined, and the primary noncovalent interactions responsible ( e.g. hydrogen bonding, solvophobicity, coulombic interactions) are identified. Noncovalent scaffold assembly in nonaqueous, ion-dense electrolytes often leads to supramolecular gel materials that can exhibit extreme stretchability, good toughness, and an ability to self-heal in many cases. After reviewing several strategies that have been recently employed for creating ionogels and eutectogels, a brief inspection of some motivating noncovalently cross-linked scaffolds reported for hydrogels is presented with the hopes that these may provide inspiration for the future design of novel ionogels and eutectogels by the materials research community.more » « less
- 
            Abstract Lightweight energy storage devices are essential for developing compact wearable and distributed electronics, and additive manufacturing offers a scalable, low‐cost approach to fabricating such devices with complex geometries. However, additive manufacturing of high‐performance, on‐demand energy storage devices remains challenging due to the need for stable, multifunctional nanomaterial inks. Herein, the development of 2‐dimensional (2D) titanium carbide (Ti3C2TxMXene) ink that is compatible with aerosol jet printing for energy storage applications is demonstrated. The developed MXene ink demonstrates long‐term chemical and physical stability, ensuring consistent printability and achieving high‐resolution prints (≈45 µm width lines) with minimal overspray. The high‐resolution aerosol‐jet printed MXene supercapacitor achieves an areal capacitance of 122 mF cm−2and a volumetric capacitance of 611 F cm−3, placing them among the highest‐performing printed supercapacitors reported to date. These findings highlight the potential of aerosol jet printing with MXene inks for on‐demand, scalable, and cost‐effective fabrication of printed electronic and electrochemical devices.more » « less
 An official website of the United States government
An official website of the United States government 
				
			 
					 
					
 
                                    