Li Peng

An iron-based green approach to 1-h production of single-layer graphene oxide

As a reliable and scalable precursor of graphene, graphene oxide (GO) is of great importance. However, the environmentally hazardous heavy metals and poisonous gases, explosion risk and long reaction times involved in the current synthesis methods of GO increase the production costs and hinder its real applications. Here we report an iron-based green strategy for the production of single-layer GO in 1 h. Using the strong oxidant K2FeO4, our approach not only avoids the introduction of polluting heavy metals and toxic gases in preparation and products but also enables the recycling of sulphuric acid, eliminating pollution. Our dried GO powder is highly soluble in water, in which it forms liquid crystals capable of being processed into macroscopic graphene fibres, films and aerogels. This green, safe, highly efficient and ultralow-cost approach paves the way to large-scale commercial applications of graphene.

Ultrastiff and Strong Graphene Fibers via Full‐Scale Synergetic Defect Engineering

Kilometer-scale continuous graphene fibers (GFs) with outstanding mechanical properties and excellent electrical conductivity are produced by high-throughput wet-spinning of graphene oxide liquid crystals followed by graphitization through a full-scale synergetic defect-engineering strategy. GFs with superior performances promise wide applications in functional textiles, lightweight motors, microelectronic devices, and so on.

Wet-Spinning of Continuous Montmorillonite-Graphene Fibers for Fire-Resistant Lightweight Conductors

All-inorganic fibers composed of neat 2D crystals possessing fascinating performance (e.g., alternately stacking layers, high mechanical strength, favorable electrical conductivity, and fire-resistance) are discussed in detail. We developed a wet-spinning assmebly strategy to achieve continuous all-inorganic fibers of montmorillonite (MMT) nanoplatelets by incorporation of a graphene oxide (GO) liquid crystal (LC) template at a rate of 9 cm/s, and the templating role of GO LC is confirmed by in situ confocal laser scanning microscopy and polarized optical microscopy inspections. After protofibers underwent thermal reduction, the obtained binary complex fibers composed of neat 2D crystals integrate the outstanding fire-retardance of MMT nanoplatelets and the excellent conductivity of graphene nanosheets. High-resolution transmission electron microscopy and scanning electron microscope observations reveal the microstructures of fibers with compactly stacking layers. MMT-graphene fibers show increaing tensile strengths (88-270 MPa) and electrical conductivities (130-10500 S/m) with increasing graphene fraction. MMT-graphene (10/90) fibers are used as fire-resistant (bearing temperature in air: 600-700 °C), lightweight (ρ < 1.62 g/cm(3)) conductors (conductivity: up to 1.04 × 10(4) S/m) in view of their superior performance in high-temperature air beyond commercial T700 carbon fibers. We attribute the fire-resistance of MMT-graphene fibers to the armor-like protection of MMT layers, which could shield graphene layers from the action of oxidative etching. The composite fibers worked well as fire-resistant conductors when being heated to glowing red by an alcohol lamp. Our GO LC-templating wet-spinning strategy may also inspire the continuous assembly of other layered crystals into high-performance composite fibers.

Ultrahigh Thermal Conductive yet Superflexible Graphene Films

Electrical devices generate heat at work. The heat should be transferred away immediately by a thermal manager to keep proper functions, especially for high-frequency apparatuses. Besides high thermal conductivity (K), the thermal manager material requires good foldability for the next generation flexible electronics. Unfortunately, metals have satisfactory ductility but inferior K (≤429 W m-1 K-1 ), and highly thermal-conductive nonmetallic materials are generally brittle. Therefore, fabricating a foldable macroscopic material with a prominent K is still under challenge. This study solves the problem by folding atomic thin graphene into microfolds. The debris-free giant graphene sheets endow graphene film (GF) with a high K of 1940 ± 113 W m-1 K-1 . Simultaneously, the microfolds render GF superflexible with a high fracture elongation up to 16%, enabling it more than 6000 cycles of ultimate folding. The large-area multifunctional GFs can be easily integrated into high-power flexible devices for highly efficient thermal management.

Graphene Oxide Liquid Crystals as a Versatile and Tunable Alignment Medium for the Measurement of Residual Dipolar Couplings in Organic Solvents

Residual dipolar couplings (RDCs) have proven to be an invaluable anisotropic NMR parameter for the structural elucidation of complex biopolymers and organic molecules. However, a remaining bottleneck limiting its wider use by organic and natural product chemists is the lack of a range of easily applicable aligning media for diverse organic solvents. In this study, graphene oxide (GO) liquid crystals (LCs) were developed to induce partial orientation of organic molecules to allow RDC measurements. These LCs were determined to be maintainable at very low concentrations (as low as 1 mg/mL, corresponding to quadrupolar (2)H splittings ranging from 2.8 to 30 Hz and maximum (13)C-(1)H dipolar couplings of 20 Hz for camphor in a CH3COCH3/water system) and to be remarkably stable and broadly compatible with aqueous and organic solvents such as dimethyl sulfoxide, CH3COCH3, and CH3CN. Moreover, compared with those for other alignment media, very clean and high-quality NMR spectra were acquired with the GO molecules in solution because of their rigidity and high molecular weight. The developed medium offers a versatile and robust method for RDC measurements that may routinize the RDC-based structure determination of organic molecules.

Solution processible hyperbranched inverse-vulcanized polymers as new cathode materials in Li–S batteries

Soluble inverse-vulcanized hyperbranched polymers (SIVHPs) were synthesized via thiol–ene addition of polymeric sulfur (S8) radicals to 1,3-diisopropenylbenzene (DIB). Benefiting from their branched molecular architecture, SIVHPs presented excellent solubility in polar organic solvents with an ultrahigh concentration of 400 mg mL−1. After end-capping by sequential click chemistry of thiol–ene and Menschutkin quaternization reactions, we obtained water soluble SIVHPs for the first time. The sulfur-rich SIVHPs were employed as solution processible cathode-active materials for Li–S batteries, by facile fluid infiltration into conductive frameworks of graphene-based ultralight aerogels (GUAs). The SIVHPs-based cells showed high initial specific capacities of 1247.6 mA h g−1 with 400 charge–discharge cycles. The cells also demonstrated an excellent rate capability and a considerable depression of shuttle effect with stable coulombic efficiency of around 100%. The electrochemical performance of SIVHP in Li–S batteries overwhelmed the case of neat sulfur, due to the chemical fixation of sulfur. The combination of high solubility, structure flexibility, and superior electrochemical performance opens a door for the promising application of SIVHPs.

A novel wet-spinning method of manufacturing continuous bio-inspired composites based on graphene oxide and sodium alginate

Nacre is a lightweight, strong, stiff, and tough material, which makes it a mimicking object for material design. Many attempts to mimic nacre by various methods resulted in the synthesis of artificial nacre with excellent properties. However, the fabrication procedure was very laborious and time-consuming due to the sequential steps, and only limited-sized materials could be obtained. Hence, a novel design enabling scalable production of high-performance artificial nacre with uniform layered structures is urgently needed. We developed a novel wet-spinning assembly technique to rapidly manufacture continuous nacremimic graphene oxide (GO, brick)-sodium alginate (SA, mortar) films and fibers with excellent mechanical properties. At high concentrations, the GO-SA mixtures spontaneously produced liquid crystals (LCs) due to the template effect of GO, and continuous, 6 m long nacre-like GO-SA films were wet-spun from the obtained GO-SA liquid crystalline (LC) dope with a speed of up to 1.5 m/min. The assembled macroscopic GO-SA composites inherited the alignment of the GO sheets from the LC phase, and their mechanical properties were investigated by a joint experimental-computational study. The tensile tests revealed that the maximum strength (σ) and Young’s modulus (E) of the obtained films reached 239.6 MPa and 22.4 GPa, while the maximum values of σ and E for the fibers were 784.9 MPa and 58 GPa, respectively. The described wet-spinning assembly method is applicable for a large-scale and fast production of high-performance continuous artificial nacre.

Group interval-controlled polymers: an example of epoxy functional polymers via step-growth thiol–yne polymerization

We have coined a new term, group interval-controlled polymers (GICPs), to describe the unique structure of macromolecules with a tunable functional group interval. The precise control of a polymer main chain structure itself is still a big challenge, let alone the purposeful control of group interval simultaneously. Here, we successfully synthesized a series of epoxy GICPs via one-step UV-triggered thiol–yne polymerization of commercial glycidyl propargyl ether and dithiols at 0 °C. Subsequently, α,ω-thiols of each epoxy GICP were capped by two allyl glycidyl ethers via a thiol–ene click reaction, affording a stable product. Their unique group interval-controlled chemical structures were confirmed by a combination of nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and pyrene-fluorescent probe tests. Moreover, the epoxy groups within the GICPs were highly reactive and could be further functionalized and turned into a diverse range of customized groups such as azide, tertiary amino, thioester, and hydroxyl, etc. Therefore, a series of GICPs with designed functional groups are readily achieved on a large scale. Our work presents a reliable synthetic methodology for GICPs, paving a new way for the precise structure control of artificial macromolecules.

Sheet Collapsing Approach for Rubber-like Graphene Papers

Understanding and modulating the conformation of graphene are pivotal in designing graphene macroscopic materials. Here, we revealed the sheet collapsing behavior of graphene oxide (GO) sheets by poor solvents in an analogy with linear macromolecules. Triggered by poor solvents, extended GO sheets in good solvents can collapse to hierarchically wrinkled conformations. The collapsing behavior of GO enabled the fabrication of amorphous self-standing GO and graphene papers with rich hierarchical wrinkles and folds over mutliple size scales. The collapsed GO and graphene papers had a rubber-like mechanical behavior with viscoelasticity. By our collapsing method, GO and graphene self-standing papers were designed to be stiff with high modulus or to become soft with low modulus of 100 MPa at a remarkably large breakage elongation up to 23%. Our philosophy of treating graphene as a 2D polymer enables the efficient control of molecular conformations of graphene and other 2D polymers and the design of macroscopic materials of 2D nanomaterials as in the polymer industry.