Abstract Liquid phase exfoliation (LPE) of graphene is a potentially scalable method to produce conductive graphene inks for printed electronic applications. Among LPE methods, wet jet milling (WJM) is an emerging approach that uses high‐speed, turbulent flow to exfoliate graphene nanoplatelets from graphite in a continuous flow manner. Unlike prior WJM work based on toxic, high‐boiling‐point solvents such as n‐methyl‐2‐pyrollidone (NMP), this study uses the environmentally friendly solvent ethanol and the polymer stabilizer ethyl cellulose (EC). Bayesian optimization and iterative batch sampling are employed to guide the exploration of the experimental phase space (namely, concentrations of graphite and EC in ethanol) in order to identify the Pareto frontier that simultaneously optimizes three performance criteria (graphene yield, conversion rate, and film conductivity). This data‐driven strategy identifies vastly different optimal WJM conditions compared to literature precedent, including an optimal loading of 15 wt% graphite in ethanol compared to 1 wt% graphite in NMP. These WJM conditions provide superlative graphene production rates of 3.2 g hr−1with the resulting graphene nanoplatelets being suitable for screen‐printed micro‐supercapacitors. Finally, life cycle assessment reveals that ethanol‐based WJM graphene exfoliation presents distinct environmental sustainability advantages for greenhouse gas emissions, fossil fuel consumption, and toxicity.
more »
« less
Facile Production of Graphenic Microsheets and Their Assembly via Water-Based, Surfactant-Aided Mechanical Deformations
Expandable graphite (EG) and few-layer graphene (FLG) have proven to be instrumental materials for various applications. The production of EG and FLG has been limited to batch processes using numerous intercalating agents, especially organic acids. In this study, a Taylor−Couette reactor (TCR) setup is used to expand and exfoliate natural graphite and produce a mixture of EG and FLG in aqueous solutions using an amphiphilic dispersant and a semiflexible stabilizer. Laminar Couette flow structure and high shear rates are achieved via the rotation of the outer cylinder while the inner cylinder is still, which circumvents vortex formation because of the suppression of centrifugal forces. Our results reveal that the level of expansion and exfoliation using an aqueous solution and a TCR is comparable to that using commercial EG (CEG) synthesized by intercalating sulfuric acid. More importantly, the resultant EG and FLG flakes are more structurally homogeneous than CEG, the ratio of FLG to EG increases with increasing shearing time, and the produced FLG sheets exhibit large lateral dimensions (>10 μm). The aqueous solutions of EG and FLG are wet-spun to produce ultralight fibers with a bulk density of 0.35 g/cm3. These graphene fibers exhibit a mechanical strength of 0.5 GPa without any modification or thermal treatment, which offers great potential in light-weight composite applications. KEYWORDS: graphene, graphite, Taylor−Couette, exfoliation, expansion, fiber
more »
« less
- Award ID(s):
- 1719875
- PAR ID:
- 10146526
- Date Published:
- Journal Name:
- ACS applied materials interfaces
- Volume:
- 12
- Issue:
- 7
- ISSN:
- 1944-8244
- Page Range / eLocation ID:
- 8944-8951
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Na-ion batteries (NIBs) are proposed as a promising candidate for beyond Li-ion chemistries, however, a key challenge associated with NIBs is the inability to achieve intercalation in graphite anodes. This phenomenon has been investigated and is believed to arise due to the thermodynamic instability of Na-intercalated graphite. We have recently demonstrated theoretical calculations showing it is possible to achieve thermodynamically stable Na-intercalated graphene structures with a fluorine surface modifier. Here, we present experimental evidence that Na + intercalation is indeed possible in fluorinated few-layer graphene (F-FLG) structures using cyclic voltammetry (CV), ion-sensitive scanning electrochemical microscopy (SECM) and in situ Raman spectroscopy. SECM and Raman spectroscopy confirmed Na + intercalation in F-FLG, while CV measurements allowed us to quantify Na-intercalated F-FLG stoichiometries around NaC 14–18 . These stoichiometries are higher than the previously reported values of NaC 186 in graphite. Our experiments revealed that reversible Na + ion intercalation also requires a pre-formed Li-based SEI in addition to the surface fluorination, thereby highlighting the critical role of SEI in controlling ion-transfer kinetics in alkali-ion batteries. In summary, our findings highlight the use of surface modification and careful study of electrode-electrolyte interfaces and interphases as an enabling strategy for NIBs.more » « less
-
Dichtel, William R. (Ed.)The ability of lotus leaves to repel water is desired in numerous applications, such as self-cleaning surfaces, biomedical devices, and naval vessels. Creating materials that mimic the hierarchical structure and surface chemistry of lotus leaves requires multistep processes that are impractical for the mass production of nonwettable products. Superhydrophobic surfaces have been created using graphene. However, graphene sheets obtained through graphite exfoliation or deposition on substrates are not superhydrophobic and require additional processes to achieve lotus-like water repellency. In this work, we show that graphene produced in the gas phase is inherently superhydrophobic. Gas-phase-synthesized graphene (GSG) and lotus leaves have fundamentally different structures, yet water droplets on both materials exhibit comparable contact angles, roll-off angles, and bouncing characteristics. Furthermore, hydrophilic surfaces become superhydrophobic when covered with GSG. The substrate-free synthesis of GSG is straightforward and sustainable, which could enable the manufacturing of a diverse range of water-repellent technologies.more » « less
-
W e present a scalable solution-processing method for fabricating high-quality graphene and graphene/1T-MoS 2 heterostructure films. The process begins with the synthesis of potassium-intercalated graphite (KC 8 ), which is exfoliated in tetrahydrofuran (THF) to produce stable dispersions of negatively charged (electron rich) graphene sheets. The graphene is subsequently transferred to water, forming a surfactant-free aqueous dispersion suitable for creating homogenous graphene films via vacuum filtration and stamping. Additionally, graphene is combined with 1T-MoS 2 nanosheets to fabricate graphene/1T-MoS 2 bulk heterostructure films. Comprehensive characterization, including X-ray diffraction (XRD), absorption spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy ( TEM), Raman spectroscopy, and X-ray photon emission spectroscopy (XPS), reveals that the heterostructure films exhibit enhanced optical and electronic properties, including improved light absorption, which could lead to novel photo-responsive devices. Raman spectroscopy shows significant changes in the graphene’s structural a nd electronic properties upon interaction with MoS 2 , indicating strong interlayer coupling and potential charge transfer between the layered components. The g raphene films demonstrate highly sensitive detection of dopamine (DA), while the graphene/1T-MoS 2 b ulk heterostructure films exhibit capacitance values up to 3 8.3 Fg − 1 at 5 mV/s in non-aqueous electrolytes. These results highlight the potential of these films for advanced applications in molecular sensing and energy storage.more » « less
-
Abstract Graphite is a commonly used raw material across many industries and the demand for high‐quality graphite has been increasing in recent years, especially as a primary component for lithium‐ion batteries. However, graphite production is currently limited by production shortages, uneven geographical distribution, and significant environmental impacts incurred from conventional processing. Here, an efficient method of synthesizing biomass‐derived graphite from biochar is presented as a sustainable alternative to natural and synthetic graphite. The resulting bio‐graphite equals or exceeds quantitative quality metrics of spheroidized natural graphite, achieving a RamanID/IGratio of 0.051 and crystallite size parallel to the graphene layers (La) of 2.08 µm. This bio‐graphite is directly applied as a raw input to liquid‐phase exfoliation of graphene for the scalable production of conductive inks. The spin‐coated films from the bio‐graphene ink exhibit the highest conductivity among all biomass‐derived graphene or carbon materials, reaching 3.58 ± 0.16 × 104S m−1. Life cycle assessment demonstrates that this bio‐graphite requires less fossil fuel and produces reduced greenhouse gas emissions compared to incumbent methods for natural, synthesized, and other bio‐derived graphitic materials. This work thus offers a sustainable, locally adaptable solution for producing state‐of‐the‐art graphite that is suitable for bio‐graphene and other high‐value products.more » « less
An official website of the United States government

