Rechargeable Zinc-Air Batteries: Advances, Challenges, and Prospects.

Rechargeable zinc-air batteries (Re-ZABs) are one of the most promising next-generation batteries that can hold more energy while being cost-effective and safer than existing devices. Nevertheless, zinc dendrites, non-portability, and limited charge-discharge cycles have long been obstacles to the commercialization of Re-ZABs. Over the past 30 years, milestone breakthroughs have been made in technical indicators (safety, high energy density, and long battery life), battery components (air cathode, zinc anode, and gas diffusion layer), and battery configurations (flexibility and portability), however, a comprehensive review on advanced design strategies for Re-ZABs system from multiple angles is still lacking. This review underscores the progress and strategies proposed so far to pursuit the high-efficiency Re-ZABs system, including the aspects of rechargeability (from primary to rechargeable), air cathode (from unifunctional to bifunctional), zinc anode (from dendritic to stable), electrolytes (from aqueous to non-aqueous), battery configurations (from non-portable to portable), and industrialization progress (from laboratorial to practical). Critical appraisals of the advanced modification approaches (such as surface/interface modulation, nanoconfinement catalysis, defect electrochemistry, synergistic electrocatalysis, etc.) are highlighted for cost-effective flexible Re-ZABs with good sustainability and high energy density. Finally, insights are further rendered properly for the future research directions of advanced zinc-air batteries.

Synthesis and Catalytic Degradation of PEF, ENR, and CIP by g-C3N4/TCNQ/Eu Composite.

By using melamine as a precursor for the copolymerization process, g-C3N4 and g-C3N4/TCNQ/Eu complexes with various amounts of doping were created. These complexes were then examined using XRD, FT-IR, SEM, TEM, XPS, PL, UV-vis, and I-T. The degradation rates of pefloxacin (PEF), enrofloxacin (ENR), and ciprofloxacin (CIP) were 91.1%, 90.8%, and 93.2% under visible light (λ > 550 nm). The photocatalytic performance of the composite was analyzed, and the best effect was obtained for CIP photocatalysis when Eu doping was 3 mg at 20 °C and pH 7. Kinetic analysis showed that there was a linear relationship between the sample and the photocatalytic time, and the degradation rate was about 5 times that of g-C3N4. The cyclic stability of the g-C3N4/TCNQ/Eu composite sample was found to be good through repeated experiments. UPLC-MS visualizes the degradation process of CIP. The extremely low stability of piperazine ring induced subsequent degradation, followed by the fracture of quinolone ring promoting the complete decomposition of CIP.

ZnO QDs/GO/g-C3N4 Preparation and Photocatalytic Properties of Composites.

Using an ultrasound-assisted chemical technique, ZnO quantum dot and ZnO composites were created. The optical characteristics and structural details of these composites were examined using TEM, XRD, XPS, FT-IR, UV-vis, and BET. The results revealed that both the ZnO quantum dot composite and ZnO composite exhibited outstanding optical properties, making them suitable for photocatalytic reactions. In order to analyze the photocatalytic performance, a degradation experiment was conducted using Rhodamine B solution as the simulation dye wastewater. The experiment demonstrated that the degradation of Rhodamine B followed the first-order reaction kinetics equation when combined with the photocatalytic reaction kinetics. Moreover, through cyclic stability testing, it was determined that the ZnO QDs-GO-g-C3N4 composite sample showed good stability and could be reused. The degradation rates of Rhodamine B solution using ZnO-GO-g-C3N4 and ZnO QDs-GO-g-C3N4 reached 95.25% and 97.16%, respectively. Furthermore, free-radical-trapping experiments confirmed that ·O2- was the main active species in the catalytic system and its photocatalytic mechanism was elucidated. The photocatalytic oxidation of ZnO quantum dots in this study has important reference value and provides a new idea for the subsequent research.

Nonstoichiometric Scandium Oxide Hybridized in N-Doped Porous Graphitic Carbon Promotes the Rate Capability of Lithium-Sulfur Batteries.

Nonstoichiometric compounds are widely used in contemporary energy technologies due to their high surface polarity, tailored electronic structure, high electrical conductivity, and other enhanced properties. However, the preparation of such nonstoichiometric compounds can be complicated and, in some cases, uncontrollable and dangerous. Here, we report a "one-pot" strategy for synthesizing N-doped porous graphitic carbon that is hybridized with nonstoichiometric scandium oxide (denoted as ScO0.95@N-PGC) and show that the composite significantly promotes sulfur cathode kinetics in lithium-sulfur (Li-S) batteries. The synthesis of the ScO0.95@N-PGC composite entails heating a porous dry gel that consists of a C source (glucose), a N source (dicyandiamide), and a Sc source (Sc(NO3)3·H2O). Thermally decomposing the dicyandiamide creates a highly reductive atmosphere that simultaneously affords the hypoxic state of the ScO0.95 and dopes the carbon matrix with nitrogen. Density functional theory reveals the presence of oxygen vacancies that enable the ScO0.95 crystals to function as excellent electrical conductors, exhibit enhanced adsorption toward polysulfides, and accelerate the cathode reactions by lowering the corresponding activation energies. Moreover, Li-S cells prepared from the ScO0.95@N-PGC composite display a high specific capacity (1046 mA h g-1 at 0.5 C), an outstanding cycling stability (641 mA h g-1 after 1000 charge-discharge cycles at 0.5 C, a capacity decay of 0.038% per cycle), and a particularly outstanding rate capability (438 mA h g-1 at 8 C). The methodology described establishes a sustainable approach for synthesizing nonstoichiometric compounds while broadening their potential utility in a broad range of energy technologies.

Growing Electrocatalytic Conjugated Microporous Polymers on Self-Standing Carbon Nanotube Films Promotes the Rate Capability of Li-S Batteries.

Lithium-sulfur (Li-S) batteries hold great promise for widespread application on account of their high theoretical energy density (2600 Wh kg-1 ) and the advantages of sulfur. Practical use, however, is impeded by the shuttle effect of polysulfides along with sluggish cathode kinetics. it is reported that such deleterious issues can be overcome by using a composite film (denoted as V-CMP@MWNT) that consists of a conjugated microporous polymer (CMP) embedded with vanadium single-atom catalysts (V SACs) and a network of multi-walled carbon nanotubes (MWNTs). V-CMP@MWNT films are fabricated by first electropolymerizing a bidentate ligand designed to coordinate to V metals on self-standing MWNT films followed by treating the CMP with a solution containing V ions. Li-S cells containing a V-CMP@MWNT film as interlayer exhibit outstanding performance metrics including a high cycling stability (616 mA h g-1 at 0.5 C after 1000 cycles) and rate capability (804 mA h g-1 at 10 C). An extraordinary area-specific capacity of 13.2 mA h cm-2 is also measured at a high sulfur loading of 12.2 mg cm-2 . The underlying mechanism that enables the V SACs to promote cathode kinetics and suppress the shuttle effect is elucidated through a series of electrochemical and spectroscopic techniques.

A Space-Confined Polymerization Templated by Ice Enables Large-Scale Synthesis of Two-Dimensional Polymer Sheets.

Despite significant progress in the preparation and characterization of two-dimensional (2D) materials, the synthesis of 2D organic materials remains challenging. Here, we report a novel space-confined polymerization method that enables the large-scale synthesis of 2D sheets of a functional conjugated polymer, namely, poly(3,4-ethylenedioxythiophene) (PEDOT). A key step in this method is the confinement of monomer to the boundaries of ice crystals using micelles. This spatial confinement directs the polymerization to form 2D PEDOT sheets with high crystallinity and controlled morphology. Supercapacitors prepared from the 2D PEDOT sheets exhibit outstanding performance metrics. In aqueous electrolyte, a high areal specific capacitance of 898 mF cm-2 at 0.2 mA cm-2 along with an excellent rate capability is achieved (e.g., capacitance retention of 67.6 % at a 50-fold higher current). Moreover, the 2D PEDOT-based supercapacitors exhibit outstanding cycling stability (capacitance retention of 98.5 % after 30,000 cycles). Device performance is further improved when an organic electrolyte is used.

P-Doping a Porous Carbon Host Promotes the Lithium Storage Performance of Red Phosphorus.

Red phosphorus (RP) is a promising anode material for use in lithium-ion batteries (LIBs) due to its high theoretical specific capacity (2596 mA h g-1). However, the practical use of RP-based anodes has been challenged by the material's low intrinsic electrical conductivity and poor structural stability during lithiation. Here, we describe a phosphorus-doped porous carbon (P-PC) and disclose how the dopant improves the Li storage performance of RP that was incorporated into the P-PC (designated as RP@P-PC). P-doping porous carbon was achieved using an in situ method wherein the heteroatom was added as the porous carbon was being formed. The phosphorus dopant effectively improves the interfacial properties of the carbon matrix as subsequent RP infusion results in high loadings, small particle sizes, and uniform distribution. In half-cells, an RP@P-PC composite was found to exhibit outstanding performance in terms of the ability to store and utilize Li. The device delivered a high specific capacitance and rate capability (1848 and 1111 mA h g-1 at 0.1 and 10.0 A g-1, respectively) as well as excellent cycling stability (1022 mA h g-1 after 800 cycles at 2.0 A g-1). Exceptional performance metrics were also measured when the RP@P-PC was used as an anode material in full cells that contained lithium iron phosphate as the cathode material. The methodology described can be extended to the preparation of other P-doped carbon materials that are employed in contemporary energy storage applications.

Carbon-Based Materials as Lithium Hosts for Lithium Batteries.

Lithium (Li) metal has attracted significant attention in areas that range from basic research to various commercial applications due to its high theoretical specific capacity (3860 mA h g-1 ) and low electrochemical potential (-3.04 vs. standard hydrogen electrode). However, dendrites often form on the surfaces of Li metal anodes during cycling and thus lead to battery failure and, in some cases, raise safety concerns. To overcome this problem, a variety of approaches that vary the electrolyte, membrane, and/or anode have been proposed. Among these efforts, the use of three-dimensional frameworks as Li hosts, which can homogenize and minimize the current density at the anode surface, is an effective approach to suppress the formation of Li dendrites. Herein, we describe the development of using carbon-based materials as Li hosts. While these materials can be fabricated into a variety of porous structures, they have a number of intrinsic advantages including low costs, high specific surface areas, high electrical conductivities, and wide electrochemical stabilities. After briefly summarizing the formation mechanisms of Li dendrites, various methods for controlling structural and surface chemistry will be described for different types of carbon-based materials from the viewpoint of improving their performance as Li hosts. Finally, we provide perspective on the future development of Li host materials needed to meet the requirements for their use in flexible and wearable devices and other contemporary energy storage techniques.

Encoding Enantiomeric Molecular Chiralities on Graphene Basal Planes.

Graphene has demonstrated broad applications due to its prominent properties. Its molecular structure makes graphene achiral. Here, we propose a direct way to prepare chiral graphene by transferring chiral structural conformation from chiral conjugated amino acids onto graphene basal plane through π-π interaction followed by thermal fusion. Using atomic resolution transmission electron microscopy, we estimated an areal coverage of the molecular imprints (chiral regions) up to 64 % on the basal plane of graphene (grown by chemical vapor deposition). The high concentration of molecular imprints in their single layer points to a close packing of the deposited amino acid molecules prior to "thermal fusion". Such "molecular chirality-encoded graphene" was tested as an electrode in electrochemical enantioselective recognition. The chirality-encoded graphene might find use for other chirality-related studies and the encoding procedure might be extended to other two-dimensional materials.

Single-Atom Catalyst Aggregates: Size-Matching is Critical to Electrocatalytic Performance in Sulfur Cathodes.

Electrocatalysis is critical to the performance displayed by sulfur cathodes. However, the constituent electrocatalysts and the sulfur reactants have vastly different molecular sizes, which ultimately restrict electrocatalysis efficiency and hamper device performance. Herein, the authors report that aggregates of cobalt single-atom catalysts (SACs) attached to graphene via porphyrins can overcome the challenges associated with the catalyst/reactant size mismatch. Atomic-resolution transmission electron microscopy and X-ray absorption spectroscopy measurements show that the Co atoms present in the SAC aggregates exist as single atoms with spatially resolved dimensions that are commensurate the sulfur species found in sulfur cathodes and thus fully accessible to enable 100% atomic utilization efficiency in electrocatalysis. Density functional theory calculations demonstrate that the Co SAC aggregates can interact with the sulfur species in a synergistic manner that enhances the electrocatalytic effect and promote the performance of sulfur cathodes. For example, Li-S cells prepared from the Co SAC aggregates exhibit outstanding capacity retention (i.e., 505 mA h g-1 at 0.5 C after 600 cycles) and excellent rate capability (i.e., 648 mA h g-1 at 6 C). An ultrahigh area specific capacity of 12.52 mA h cm-2 is achieved at a high sulfur loading of 11.8 mg cm-2 .

Regulating Lithium Plating and Stripping by Using Vertically Aligned Graphene/CNT Channels Decorated with ZnO Particles.

Lithium (Li) metal is regarded as the ultimate anode material for use in Li batteries due to its high theoretical capacity (3860 mA h g-1 ). However, the Li dendrites that are generated during iterative Li plating/stripping cycles cause poor cycling stability and even present safety risks, and thus severely handicap the commercial utility of Li metal anodes. Herein, we describe a graphene and carbon nanotube (CNT)-based Li host material that features vertically aligned channels with attached ZnO particles (designated ZnO@G-CNT-C) and show that the material effectively regulates Li plating and stripping. ZnO@G-CNT-C is prepared from an aqueous suspension of Zn(OAc)2 , CNTs, and graphene oxide by using ice to template channel growth. ZnO@G-CNT-C was found to be mechanically robust and capable of guiding Li deposition on the inner walls of the channels without the formation of Li dendrites. When used as an electrode, the material exhibits relatively low polarization for Li plating, fast Li-ion diffusion, and high Coulombic efficiency, even over hundreds of Li plating/stripping cycles. Moreover, full cells prepared with ZnO@G-CNT-C as Li host and LiFePO4 as cathode exhibit outstanding performance in terms of specific capacity (155.9 mA h g-1 at 0.5 C), rate performance (91.8 mA h g-1 at 4 C), cycling stability (109.4 mA h g-1 at 0.5 C after 800 cycles). The methodology described can be readily adapted to enable the use of carbon-based electrodes with well-defined channels in a wide range of contemporary applications that pertain to energy storage and delivery.

Ice-Templated Large-Scale Preparation of Two-Dimensional Sheets of Conjugated Polymers: Thickness-Independent Flexible Supercapacitance.

Two-dimensional (2D) organic materials hold great promise for use in a multitude of contemporary applications due to their outstanding chemical and physical properties. Herein, 2D sheets of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) are prepared from a commercially available PEDOT:PSS suspension using ice as a template. The 2D PEDOT:PSS sheets grow in the boundaries of ice crystals as the polymers are "squeezed" out of the suspension when the water solidifies. The mechanical robustness of the sheets can be enhanced by incorporating WO3 nanowires, and the PSS component can be conveniently removed with a concentrated solution of H2SO4 to afford stable suspensions of PEDOT or WO3@PEDOT sheets, either of which can be converted into flexible films with tunable thicknesses via filtration. Swagelok- or pouch-type supercapacitor devices prepared from the WO3@PEDOT films exhibit outstanding energy-storage characteristics, including high rate capability, thickness-independent energy storage (e.g., 701 mF cm-2 is achieved with a 1-mm-thick film), high resistance toward mechanical deformation, and good cycling stability. Additionally, a high energy density of 0.083 mWh cm-2 is measured for a device prepared using a 1-mm-thick film at a high power density of 10 mW cm-2. The methodology described establishes an efficient and readily scalable approach for accessing 2D organic sheets.

Kinetic Enhancement of Sulfur Cathodes by N-Doped Porous Graphitic Carbon with Bound VN Nanocrystals.

The reaction kinetics of sulfur cathodes generally control the performance of lithium-sulfur (Li-S) batteries. Here, N-doped porous graphitic carbon with bound VN nanocrystals (3D VN@N-PGC), which is synthesized in one pot by heating a mixture of glucose as C source, urea as N source, and NH4 VO3 as V source, is reported to be an superior electrocatalytic cathode host for Li-S batteries. Notably, the VN nanocrystals, strongly bound to the N-PGC network, form via in situ reactions among the thermolytic products of starting materials. The dopant N atoms and bound VN nanocrystals exhibit synergistic electrocatalytic effects to promote the cathode reactions of the Li-S cells. The observed enhancements are supported by density functional theory simulations and by the observation of electrocatalytic N- and V-intermediate species, via X-ray absorption near-edge structure spectroscopy. Li-S cells assembled using 3D VN@N-PGC as cathode host exhibit superior performance in terms of specific capacity (1442 mA h g-1 at 0.1 C), rate capability (641 mA h g-1 at 4 C), and cycle life (466 mA h g-1 after 1700 cycles at 2 C, corresponding to a capacity decay of 0.020% per cycle). The one-pot methodology is facile and scalable and offers a new approach for synthesis of various metal nitride-containing materials for other electrocatalytic applications.

Covalent Confinement of Sulfur Copolymers onto Graphene Sheets Affords Ultrastable Lithium-Sulfur Batteries with Fast Cathode Kinetics.

Lithium-sulfur (Li-S) batteries have received significant attention due to the high theoretical specific capacity of sulfur (1675 mA h g-1). However, the practical applications are often handicapped by sluggish electrochemical kinetics and the "shuttle effect" of electrochemical intermediate polysulfides. Herein, we propose an in-situ copolymerization strategy for covalently confining a sulfur-containing copolymer onto reduced graphene oxide (RGO) to overcome the aforementioned challenges. The copolymerization was performed by heating elemental sulfur and isopropenylphenyl-functionalized RGO to afford a sulfur-containing copolymer, that is, RGO- g-poly(S- r-IDBI), which is featured by a high sulfur content and uniform distribution of the poly(S- r-IDBI) on RGO sheets. The covalent confinement of poly(S- r-IDBI) onto RGO sheets not only enhances the Li+ diffusion coefficients by nearly 1 order of magnitude, but also improves the mechanical properties of the cathodes and suppresses the shuttle effect of polysulfides. As a result, the RGO- g-poly(S- r-IDBI) cathode exhibits an enhanced sulfur utilization rate (10% higher than that of an elemental sulfur cathode at 0.1C), an improved rate capacity (688 mA h g-1 for the RGO- g-poly(S- r-IDBI) cathode vs 400 mA h g-1 for an elemental sulfur cathode at 1C), and a high cycling stability (a capacity decay of 0.021% per cycle, less than one-tenth of that measured for an elemental sulfur cathode).

MoS2 nanotubes loaded with TiO2 nanoparticles for enhanced electrocatalytic hydrogen evolution.

Efficient and stable non-precious metal catalysts composed of earth-abundant elements are crucial to the hydrogen evolution reaction (HER) in high-energy conversion efficiency. Herein, TiO2/MoS2-NTs catalyst, in which the MoS2 nanotubes were loaded with TiO2 nanoparticles, have been synthesized via a facile solvothermal and hydrothermal method. The as-prepared TiO2/MoS2-NTs electrocatalyst demonstrated enhanced electrocatalytic hydrogen evolution performance compared with MoS2-NTs. Electrochemical measurements reveal the overpotential and Tafel slope of as-prepared TiO2/MoS2-NTs are -0.21 V and 42 mV dec-1. The HER improvement is proposed to be attributed to the increased edge sites results from the interfaces and synergic effect between TiO2 nanoparticles and MoS2 nanotubes.

Covalent bonding of sulfur nanoparticles to unzipped multiwalled carbon nanotubes for high-performance lithium-sulfur batteries.

The use of sulfur as a cathode material for lithium-sulfur (Li-S) batteries has attracted significant attention due to its high theoretical specific capacity (1675 mA h g-1); however, practicality is hindered by a number of obstacles, including the shuttling effect of polysulfides and the low electrical conductivity of sulfur. Herein, ball milling sulfur with unzipped multiwalled carbon nanotubes (UMWNTs) was found to covalently immobilize sulfur nanoparticles to the UMWNTs and resulted in composites (designated as S@UMWNTs) with high electrical conductivity. The unzipping degree of MWNTs was first controlled to optimize the immobilization of sulfur nanoparticles to UMWNTs and the electrochemical performance of the resulting Li-S batteries. The presence of C-S covalent bonds between the UMWNTs and sulfur nanoparticles was verified using x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy, and the formation of C-S bonds was ascribed to the reactions between the mechanically-induced sulfur radicals and the functional groups of UMWNTs. As a result, when used as a cathode material for Li-S batteries, the S@UMWNTs exhibited excellent electrochemical performance, including a good long-term cycling stability and low capacity decay (e.g., ca. 0.09% per cycle over 500 charge/discharge cycles at 1 C) due to the suppression of the shuttling effect by the C-S covalent bonds.

Synthesis of a Macroporous Conjugated Polymer Framework: Iron Doping for Highly Stable, Highly Efficient Lithium-Sulfur Batteries.

Porous conjugated polymers offer enormous potential for energy storage because of the combined features of pores and extended π-conjugated structures. However, the drawbacks such as low pore volumes and insolubilities of micro- and mesoporous conjugated polymers restrict the loading of electroactive materials and thus energy storage performance. Herein, we report the synthesis of iron-doped macroporous conjugated polymers for hosting sulfur as the cathode of high-performance lithium-sulfur (Li-S) batteries. The macroporous conjugated polymers are synthesized via in situ growth of poly(3-hexylthiophene) (P3HT) from reduced graphene oxide (RGO) sheets, followed by gelation of the composite (RGO- g-P3HT) in p-xylene and freeze-drying. The network structures of the macroporous materials can be readily tuned by controlling the chain length of P3HT grafted to RGO sheets. The large pore volumes of the macroporous RGO- g-P3HT materials (ca. 34 cm3 g-1) make them excellent frameworks for hosting sulfur as cathodes of Li-S batteries. Furthermore, incorporation of Fe into the macroporous RGO- g-P3HT cathode results in reduced polarization, enhanced specific capacity (1,288, 1,103, and 907 mA h g-1 at 0.05, 0.1, and 0.2 C, respectively), and improved cycling stability (765 mA h g-1 after 100 cycles at 0.2 C). Density functional theory calculations and in situ characterizations suggest that incorporation of Fe enhances the interactions between lithium polysulfides and the P3HT framework.

Macroporous Graphene Thin Films as Electrochemical Electrodes: Enhancing the Sensitivity for Detection of Metal Ions.

A macroporous graphene thin films coated on ITO substrates (MGTFs@ITO) have been developed as electrodes for the electrochemical detection of heavy metal ions. The MGTF@ITO electrodes were characterized by scanning electron microscopy, Raman spectroscopy and contact angle measurements. The results demonstrated that the MGTF@ITO has a high specific area with robust macroporous framework and a hydrophilic surface. The cyclic voltammetry and electrochemical impedance spectroscopy using MGTFs@ITO as electrochemical electrodes indicated enhanced currents at the redox peaks, enlarged electrochemical surface area and a decreased charge transfer resistance. Based on these outstanding properties, the MGTF@ITO electrodes exhibited excellent stripping performace for the analysis of Ag(I) with a detection limit of 0.005 µg L-1. The high sensitivity of the MGTF@ITO electrodes can be ascribed to the well defined macroporous framework, high electrical conductivity, high specific area and good wettability. The MGTF@ITO electrodes were further demonstrated applicable to the simultaneous determination of Zn(II), Cd(II), Pb(II), Cu(II) and Ag(I) ions with outstanding sensing performance.

Graphene Oxide Facilitates Solvent-Free Synthesis of Well-Dispersed, Faceted Zeolite Crystals.

Zeolites with molecular dimension pores are widely used in petrochemical and fine-chemical industries. While traditional solvothermal syntheses suffer from environmental, safety, and efficiency issues, the newly developed solvent-free synthesis is limited by zeolite crystal aggregation. Herein, we report well-dispersed and faceted silicalite ZSM-5 zeolite crystals obtained using a solvent-free synthesis facilitated by graphene oxide (GO). The selective interactions between the GO sheets and different facets, which are confirmed by molecular dynamics simulations, result in oriented growth of the ZSM-5 crystals along the c-axis. More importantly, the incorporation of GO sheets into the ZSM-5 crystals leads to the formation of mesopores. Consequently, the faceted ZSM-5 crystals exhibit hierarchical pore structures. This synthetic method is superior to conventional approaches because of the features of the ZSM-5 zeolite.

Lightweight and Ultrastrong Polymer Foams with Unusually Superior Flame Retardancy.

High-performance flame-retardant materials are urgently needed to address outstanding issues that pertain to safety. Traditional flame retardants are toxic to the environment and/or lack the physical properties required for use in many contemporary applications. Here, we show that isocyanate-based polyimide (PI) foam, a flammable material, can exhibit unusually superior flame retardancy as well as other excellent properties, such as being lightweight and displaying high mechanical strength, by incorporating red phosphorus (RP)-hybridized graphene. The covalent bonds formed between the graphene platelets and the PI matrix provide the resultant PI foam with a specific Young's modulus (83 kNm kg-1) that is comparable to or even higher than those displayed by state-of-the-art foams, including silica aerogels, polystyrene foams, and polyurethane foams. In addition, even a low content of the RP-hybridized graphene (2.2 wt %) results in an exceptionally higher limiting oxygen index (39.4) than those of traditional flame-retardant polymer-based materials (typically 20-30). The resultant PI foam also exhibits thermal insulation properties that are similar to that of air. Moreover, the RP-hybridized graphene is prepared using a one-step ball milling process in 100% yield, and does not require solvent or produce waste. The preparation of the flame-retardant PI foams can be scaled as the starting materials are commercially available and the techniques employed are industrially compatible.