Ultrahigh-throughput cross-flow filtration of solution-processed 2D materials enabled by porous ceramic membranes.

Printed electronics is a disruptive technology in multiple applications including environmental and biological sensors, flexible displays, and wearable diagnostic devices. With superlative electronic, optical, mechanical, and chemical properties, two-dimensional (2D) materials are promising candidates for printable electronic inks. While liquid-phase exfoliation (LPE) methods can produce electronic-grade 2D materials, conventional batch separation processes typically rely on centrifugation, which requires significant time and effort to remove incompletely exfoliated bulk powders, hindering the scale-up of 2D ink manufacturing. While cross-flow filtration (CFF) has emerged as a promising continuous flow separation method for solution-processed 2D nanosheets, previously demonstrated polymer CFF membranes necessitate low 2D nanosheet concentrations to avoid fouling, which ultimately limits mass throughput. Here, we demonstrate a fully flow-based, exfoliation-to-ink system for electronic-grade 2D materials using an integrated cross-flow separation and concentration system. To overcome the relatively low-throughput processing concentrations of incumbent polymer CFF membranes, we employ porous ceramic CFF membranes that are tolerant to 10-fold higher nanosheet concentrations and flow rates without compromising separation efficiency. Furthermore, we demonstrate a concentration method via cross-flow ultrafiltration, where the retentate can be directly formulated into printable inks with electronic-grade performance that meets or exceeds centrifugally produced inks. Life cycle assessment and technoeconomic analysis quantitatively confirm the advantages of ceramic versus polymer CFF membranes including reductions of 97%, 96%, 94%, and 93% for greenhouse gas emissions, water consumption, fossil fuel consumption, and specific production costs, respectively. Overall, this work presents an environmentally sustainable and cost-effective solution for the fabrication, separation, and printing of electronic-grade 2D materials.

Tailoring Electrical Properties in Carbon Nanomaterial Patterns with Multimaterial Aerosol Jet Printing.

Multimaterial aerosol jet printing offers a unique capability to freely mix inks with different chemical compositions in the aerosol phase, enabling one-step digital fabrication with tailored compositions or functionally graded structures, including in the x-y plane. Here, in situ mixing of two carbon nanomaterial inks with distinct electrical properties is demonstrated. By tailoring the mixing ratio of the constituent inks, electrical conductivity is modulated by 130×, and sheet resistance values for a single pass span approximately 2 orders of magnitude. The ability to manufacture components with tailored electrical properties offers significant value for hybrid and flexible electronic device applications, such as microelectronics packaging. Moreover, grading properties within a part provides a new dimension of design freedom for complex assemblies.

Centrifuge-Free Separation of Solution-Exfoliated 2D Nanosheets via Cross-Flow Filtration.

Solution-processed graphene is a promising material for numerous high-volume applications including structural composites, batteries, sensors, and printed electronics. However, the polydisperse nature of graphene dispersions following liquid-phase exfoliation poses major manufacturing challenges, as incompletely exfoliated graphite flakes must be removed to achieve optimal properties and downstream performance. Incumbent separation schemes rely on centrifugation, which is highly energy-intensive and limits scalable manufacturing. Here, cross-flow filtration (CFF) is introduced as a centrifuge-free processing method that improves the throughput of graphene separation by two orders of magnitude. By tuning membrane pore sizes between microfiltration and ultrafiltration length scales, CFF can also be used for efficient recovery of solvents and stabilizing polymers. In this manner, life cycle assessment and techno-economic analysis reveal that CFF reduces greenhouse gas emissions, fossil energy usage, water consumption, and specific production costs of graphene manufacturing by 57%, 56%, 63%, and 72%, respectively. To confirm that CFF produces electronic-grade graphene, CFF-processed graphene nanosheets are formulated into printable inks, leading to state-of-the-art thin-film conductivities exceeding 104 S m-1 . This CFF methodology can likely be generalized to other van der Waals layered solids, thus enabling sustainable manufacturing of the diverse set of applications currently being pursued for 2D materials.

Systematic Design of a Graphene Ink Formulation for Aerosol Jet Printing.

Aerosol jet printing is a noncontact, digital, additive manufacturing technique compatible with a wide variety of functional materials. Although promising, development of new materials and devices using this technique remains hindered by limited rational ink formulation, with most recent studies focused on device demonstration rather than foundational process science. In the present work, a systematic approach to formulating a polymer-stabilized graphene ink is reported, which considers the effect of solvent composition on dispersion, rheology, wetting, drying, and phase separation characteristics that drive process outcomes. It was found that a four-component solvent mixture composed of isobutyl acetate, diglyme, dihydrolevoglucosenone, and glycerol supported efficient ink atomization and controlled in-line drying to reduce overspray and wetting instabilities while maintaining high resolution and electrical conductivity, thus overcoming a trade-off in deposition rate and resolution common to aerosol jet printing. Biochemical sensors were printed for amperometric detection of the pesticide parathion, exhibiting a detection limit of 732 nM and a sensitivity of 34 nA µM-1, demonstrating the viability of this graphene ink for fabricating functional electronic devices.