Nondestructive flash cathode recycling.

Effective recycling of end-of-life Li-ion batteries (LIBs) is essential due to continuous accumulation of battery waste and gradual depletion of battery metal resources. The present closed-loop solutions include destructive conversion to metal compounds, by destroying the entire three-dimensional morphology of the cathode through continuous thermal treatment or harsh wet extraction methods, and direct regeneration by lithium replenishment. Here, we report a solvent- and water-free flash Joule heating (FJH) method combined with magnetic separation to restore fresh cathodes from waste cathodes, followed by solid-state relithiation. The entire process is called flash recycling. This FJH method exhibits the merits of milliseconds of duration and high battery metal recovery yields of ~98%. After FJH, the cathodes reveal intact core structures with hierarchical features, implying the feasibility of their reconstituting into new cathodes. Relithiated cathodes are further used in LIBs, and show good electrochemical performance, comparable to new commercial counterparts. Life-cycle-analysis highlights that flash recycling has higher environmental and economic benefits over traditional destructive recycling processes.

Battery metal recycling by flash Joule heating.

The staggering accumulation of end-of-life lithium-ion batteries (LIBs) and the growing scarcity of battery metal sources have triggered an urgent call for an effective recycling strategy. However, it is challenging to reclaim these metals with both high efficiency and low environmental footprint. We use here a pulsed dc flash Joule heating (FJH) strategy that heats the black mass, the combined anode and cathode, to >2100 kelvin within seconds, leading to ~1000-fold increase in subsequent leaching kinetics. There are high recovery yields of all the battery metals, regardless of their chemistries, using even diluted acids like 0.01 M HCl, thereby lessening the secondary waste stream. The ultrafast high temperature achieves thermal decomposition of the passivated solid electrolyte interphase and valence state reduction of the hard-to-dissolve metal compounds while mitigating diffusional loss of volatile metals. Life cycle analysis versus present recycling methods shows that FJH significantly reduces the environmental footprint of spent LIB processing while turning it into an economically attractive process.

Flash Recycling of Graphite Anodes.

The ever-increasing production of commercial lithium-ion batteries (LIBs) will result in a staggering accumulation of waste when they reach their end of life. A closed-loop solution, with effective recycling of spent LIBs, will lessen both the environmental impacts and economic cost of their use. Presently, <5% of spent LIBs are recycled and the regeneration of graphite anodes has, unfortunately, been mostly overlooked despite the considerable cost of battery-grade graphite. Here, an ultrafast flash recycling method to regenerate the graphite anode is developed and valuable battery metal resources are recovered. Selective Joule heating is applied for only seconds to efficiently decompose the resistive impurities. The generated inorganic salts, including lithium, cobalt, nickel, and manganese, can be easily recollected from the flashed anode waste using diluted acid, specifically 0.1 m HCl. The flash-recycled anode preserves the graphite structure and is coated with a solid-electrolyte-interphase-derived carbon shell, contributing to high initial specific capacity, superior rate performance, and cycling stability, when compared to anode materials recycled using a high-temperature-calcination method. Life-cycle-analysis relative to current graphite production and recycling methods indicate that flash recycling can significantly reduce the total energy consumption and greenhouse gas emission while turning anode recycling into an economically advantageous process.

Robust Superhydrophobic Surfaces via the Sand-In Method.

Superhydrophobic surfaces have gained sustained attention because of their extensive applications in the fields of self-cleaning, anti-icing, and drag reduction systems. Water droplets must have large apparent contact angle (CA) (>150°) and small CA hysteresis (<10°) on these surfaces. However, previous research usually involves complex fabrication strategies to modify the surface wettability. It is also challenging to maintain the temporal and mechanical stability of the delicate surface textures. Here, we develop a one-step solvent-free sand-in method to fabricate robust superhydrophobic surfaces directly atop various substrates with an apparent CA up to ∼163.8° and hysteresis less than 5°. The water repellency can withstand 100 Scotch tape peeling tests and remain stable after being stored under ambient humid conditions in Houston, Texas, for 18 months or being heated at 130 °C in air for 24 h. The superhydrophobic surfaces have excellent anti-icing ability, including a ∼2.6× longer water freezing time and ∼40% smaller ice adhesion strength with the temperature as low as -35 °C. Since the surface layers are fabricated by sanding the substrates with the powder additives, the surface damage can be repaired by a direct re-sanding treatment with the same powder additives. Further sand-in condition screenings broaden surface wettability from hydrophilic to superhydrophobic. The sand-in method induces the surface modification and the formation of the tribofilm. Surface and materials characterizations reveal that both microstructures and nanoscale asperities of the tribofilms contribute to the robust superhydrophobic features of sanded surfaces.

Turbostratic Boron-Carbon-Nitrogen and Boron Nitride by Flash Joule Heating.

Turbostratic layers in 2D materials have an interlayer misalignment. The lack of alignment expands the intrinsic interlayer distances and weakens the optical and electronic interactions between adjacent layers. This introduces properties distinct from those structures with well-aligned lattices and strong coupling interactions. However, direct and rapid synthesis of turbostratic materials remains a challenge owing to their thermodynamically metastable properties. Here, a flash Joule heating (FJH) method to achieve bulk synthesis of boron-carbon-nitrogen ternary compounds with turbostratic structures by a kinetically controlled ultrafast cooling process that takes place within milliseconds (103  to 104 K s-1 ) is reported. Theoretical calculations support the existence of turbostratic structures and provide estimates of the energy barriers with respect to conversion into the corresponding well-aligned counterparts. When using non-carbon conductive additives, a direct synthesis of boron nitride is possible. The turbostratic nature facilitates mechanical exfoliation and more stable dispersions. Accordingly, the addition of flash products to a poly(vinyl alcohol) nanocomposite film coating a copper surface greatly improves the copper's resistance to corrosion in 0.5 m sulfuric acid or 3.5 wt% saline solution. FJH allows the use of bulk materials as reactants and provides a rapid approach to large quantities of the hitherto hard-to-access turbostratic materials.

Heteroatom-Doped Flash Graphene.

Heteroatom doping can effectively tailor the local structures and electronic states of intrinsic two-dimensional materials, and endow them with modified optical, electrical, and mechanical properties. Recent studies have shown the feasibility of preparing doped graphene from graphene oxide and its derivatives via some post-treatments, including solid-state and solvothermal methods, but they require reactive and harsh reagents. However, direct synthesis of various heteroatom-doped graphene in larger quantities and high purity through bottom-up methods remains challenging. Here, we report catalyst-free and solvent-free direct synthesis of graphene doped with various heteroatoms in bulk via flash Joule heating (FJH). Seven types of heteroatom-doped flash graphene (FG) are synthesized through millisecond flashing, including single-element-doped FG (boron, nitrogen, oxygen, phosphorus, sulfur), two-element-co-doped FG (boron and nitrogen), as well as three-element-co-doped FG (boron, nitrogen, and sulfur). A variety of low-cost dopants, such as elements, oxides, and organic compounds are used. The graphene quality of heteroatom-doped FG is high, and similar to intrinsic FG, the material exhibits turbostraticity, increased interlayer spacing, and superior dispersibility. Electrochemical oxygen reduction reaction of different heteroatom-doped FG is tested, and sulfur-doped FG shows the best performance. Lithium metal battery tests demonstrate that nitrogen-doped FG exhibits a smaller nucleation overpotential compared to Cu or undoped FG. The electrical energy cost for the synthesis of heteroatom-doped FG synthesis is only 1.2 to 10.7 kJ g-1, which could render the FJH method suitable for low-cost mass production of heteroatom-doped graphene.

Phase controlled synthesis of transition metal carbide nanocrystals by ultrafast flash Joule heating.

Nanoscale carbides enhance ultra-strong ceramics and show activity as high-performance catalysts. Traditional lengthy carburization methods for carbide syntheses usually result in coked surface, large particle size, and uncontrolled phase. Here, a flash Joule heating process is developed for ultrafast synthesis of carbide nanocrystals within 1 s. Various interstitial transition metal carbides (TiC, ZrC, HfC, VC, NbC, TaC, Cr2C3, MoC, and W2C) and covalent carbides (B4C and SiC) are produced using low-cost precursors. By controlling pulse voltages, phase-pure molybdenum carbides including ß-Mo2C and metastable α-MoC1-x and η-MoC1-x are selectively synthesized, demonstrating the excellent phase engineering ability of the flash Joule heating by broadly tunable energy input that can exceed 3000 K coupled with kinetically controlled ultrafast cooling (>104 K s-1). Theoretical calculation reveals carbon vacancies as the driving factor for topotactic transition of carbide phases. The phase-dependent hydrogen evolution capability of molybdenum carbides is investigated with ß-Mo2C showing the best performance.

Machine Learning Guided Synthesis of Flash Graphene.

Advances in nanoscience have enabled the synthesis of nanomaterials, such as graphene, from low-value or waste materials through flash Joule heating. Though this capability is promising, the complex and entangled variables that govern nanocrystal formation in the Joule heating process remain poorly understood. In this work, machine learning (ML) models are constructed to explore the factors that drive the transformation of amorphous carbon into graphene nanocrystals during flash Joule heating. An XGBoost regression model of crystallinity achieves an r2 score of 0.8051 ± 0.054. Feature importance assays and decision trees extracted from these models reveal key considerations in the selection of starting materials and the role of stochastic current fluctuations in flash Joule heating synthesis. Furthermore, partial dependence analyses demonstrate the importance of charge and current density as predictors of crystallinity, implying a progression from reaction-limited to diffusion-limited kinetics as flash Joule heating parameters change. Finally, a practical application of the ML models is shown by using Bayesian meta-learning algorithms to automatically improve bulk crystallinity over many Joule heating reactions. These results illustrate the power of ML as a tool to analyze complex nanomanufacturing processes and enable the synthesis of 2D crystals with desirable properties by flash Joule heating.

Ultrafast and Controllable Phase Evolution by Flash Joule Heating.

Flash Joule heating (FJH), an advanced material synthesis technique, has been used for the production of high-quality carbon materials. Direct current discharge through the precursors by large capacitors has successfully converted carbon-based starting materials into bulk quantities of turbostratic graphene by the FJH process. However, the formation of other carbon allotropes, such as nanodiamonds and concentric carbon materials, as well as the covalent functionalization of different carbon allotropes by the FJH process, remains challenging. Here, we report the solvent-free FJH synthesis of three different fluorinated carbon allotropes: fluorinated nanodiamonds, fluorinated turbostratic graphene, and fluorinated concentric carbon. This is done by millisecond flashing of organic fluorine compounds and fluoride precursors. Spectroscopic analysis confirms the modification of the electronic states and the existence of various short-range and long-range orders in the different fluorinated carbon allotropes. The flash-time-dependent relationship is further demonstrated to control the phase evolution and product compositions.

High-Resolution Laser-Induced Graphene from Photoresist.

The fabrication of patterned graphene electronics at high resolution is an important challenge for many applications in microelectronics. Here, we demonstrate the conversion of positive photoresist (PR), commonly employed in the commercial manufacture of consumer electronics, into laser-induced graphene (LIG). Sequential lasing converts the PR photopolymer first into amorphous carbon, then to photoresist-derived LIG (PR-LIG). The resulting material possesses good conductivity and is easily doped with metal or other additives for additional functionality. Furthermore, photolithographic exposure of PR prior to lasing enables the generation of PR-LIG patterns small enough to be invisible to the naked eye. By exploiting PR as a photopatternable LIG precursor, PR-LIG can be synthesized with a spatial resolution of ∼10 µm, up to 15 times smaller than conventional LIG patterning methods. The patterning of these small PR-LIG features could offer a powerful and broadly accessible strategy for the fabrication of microscale LIG-derived nanocomposites for on-chip devices.

Millisecond Conversion of Metastable 2D Materials by Flash Joule Heating.

Controllable phase engineering is vital for precisely tailoring material properties since different phase structures have various electronic states and atomic arrangements. Rapid synthesis of thermodynamically metastable materials, especially two-dimensional metastable materials, with high efficiency and low cost remains a large challenge. Here we report flash Joule heating (FJH) as an electrothermal method to achieve the bulk conversion of transition metal dichalcogenides, MoS2 and WS2, from 2H phases to 1T phases in milliseconds. The conversions can reach up to 76% of flash MoS2 using tungsten powder as conductive additive. Different degrees of phase conversion can be realized by controlling the FJH conditions, such as reaction duration and additives, which allows the study of ratio-dependent properties. First-principles calculations confirm that structural processes associated with the FJH, such as vacancy formation and charge accumulation, result in stabilization of the 1T phases. FJH offers rapid access to bulk quantities of the hitherto hard-to-access 1T phases, a promising method for further fundamental research and diverse applications of metastable phases.

Nanocars with Permanent Dipoles: Preparing for the Second International Nanocar Race.

With the desire to synthesize surface-rolling molecular machines that can be translated and rotated with extreme precision and speed, we have synthesized a series of five nanocars. Each structure features a permanent dipole moment, generated by an N,N-dimethylamino- moiety on one end of the car coupled with a nitro group on the other end. These cars are designed to be stimulated with an electric field gradient from a scanning probe microscopy tip. The nanocars all possess unexplored combinations of structural features: tert-butyl wheels, short alkyne chassis, and combination sets of wheels including one set of tert-butyl wheels and another set of larger adamantane wheels on the same car. Each of these features needs to be assessed as preparation for the second International Nanocar Race that is taking place in 2022.

Flash Graphene Morphologies.

Flash Joule heating (FJH) can convert almost any carbon-based precursor into bulk quantities of graphene. This work explores the morphologies and properties of flash graphene (FG) generated from carbon black. It is shown that FG is partially comprised of sheets of turbostratic FG (tFG) that have a rotational mismatch between neighboring layers. The remainder of the FG is wrinkled graphene sheets that resemble nongraphitizing carbon. To generate high quality tFG sheets, a FJH duration of 30-100 ms is employed. Beyond 100 ms, the turbostratic sheets have time to AB-stack and form bulk graphite. Atomistic simulations reveal that generic thermal annealing yields predominantly wrinkled graphene which displays minimal to no alignment of graphitic planes, as opposed to the high-quality tFG that might be formed under the direct influence of current conducted through the material. The tFG was easily exfoliated via shear, hence the FJH process has the potential for bulk production of tFG without the need for pre-exfoliation using chemicals or high energy mechanical shear.

Laminated Laser-Induced Graphene Composites.

Laser-induced graphene (LIG) is a porous graphene foam generated by lasing carbon-based precursors. Compositing LIG expands the spectrum of applications for which the material may be used. Techniques for scale-up of LIG composites will be essential as the technology approaches commercialization. Roll-to-roll processing is of special interest, as precisely controlled patterning can be performed in conjunction with continuous formation of composites. Here, we demonstrate a simple lamination compositing method that is compatible with roll-to-roll processing and yields functional, patterned, and multilayered LIG composites with various thermoplastic films. Multiple lamination steps are used to encapsulate LIG within composites. We also demonstrate several applications for LIG that have been enabled by the lamination compositing technique. These include robust flexible electrodes generated through laminating copper foil strips into the LIG composite, LIG-based triboelectric nanogenerators to harvest waste mechanical energy, antimicrobial LIG composite bandages with varying hydrophobicity, and LIG puncture detectors.

On the advancement of highly cited research in China: An analysis of the Highly Cited database.

This study investigates the progress of highly cited research in China from 2001 to 2016 through the analysis of the Highly Cited database. The Highly Cited database, compiled by Clarivate Analytics, is comprised of the world's most influential researchers in the 22 Essential Science Indicator fields as catalogued by the Web of Science. The database is considered an international standard for the measurement of national and institutional highly cited research output. Overall, we found a consistent and substantial increase in Highly Cited Researchers from China during the timespan. The Chinese institutions with the most Highly Cited Researchers- the Chinese Academy of Sciences, Tsinghua University, Peking University, Zhejiang University, the University of Science and Technology of China, and BGI Shenzhen- are all top ten universities or primary government research institutions. Further evaluation of separate fields of research and government funding data from the National Natural Science Foundation of China revealed disproportionate growth efficiencies among the separate divisions of the National Natural Science Foundation. The most development occurred in the fields of Chemistry, Materials Sciences, and Engineering, whereas the least development occurred in Economics and Business, Health Sciences, and Life Sciences.