Recent Advancements of Graphene-Based Materials for Zinc-Based Batteries: Beyond Lithium-Ion Batteries.

Graphene-based materials (GBMs) possess a unique set of properties including tunable interlayer channels, high specific surface area, and good electrical conductivity characteristics, making it a promising material of choice for making electrode in rechargeable batteries. Lithium-ion batteries (LIBs) currently dominate the commercial rechargeable battery market, but their further development has been hampered by limited lithium resources, high lithium costs, and organic electrolyte safety concerns. From the performance, safety, and cost aspects, zinc-based rechargeable batteries have become a promising alternative of rechargeable batteries. This review highlights recent advancements and development of a variety of graphene derivative-based materials and its composites, with a focus on their potential applications in rechargeable batteries such as LIBs, zinc-air batteries (ZABs), zinc-ion batteries (ZIBs), and zinc-iodine batteries (Zn-I2 Bs). Finally, there is an outlook on the challenges and future directions of this great potential research field.

Cross-Linked Sodium Alginate as A Multifunctional Binder to Achieve High-Rate and Long-Cycle Stability for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) hold great promise owing to the naturally abundant sodium resource and high safety. The research focus of SIBs is usually directed toward electrode materials, while the binder as an important component is rarely investigated. Herein, a cross-linked sodium alginate (SA)/graphene oxide (GO) binder is judiciously designed to serve as a robust artificial interphase on the surface of both anode and cathode of SIBs. Benefiting from the cross-linking continuous network structure as well as the highly hydrophilic nature, the SA-GO binder possesses a large tensile strength of 197.7 Mpa and a high ionic conductivity of 0.136 mS cm-1 , superior to pure SA (93.8 Mpa, 0.025 mS cm-1 ). Moreover, the structural design of SA-GO binder exhibits a strong binding ability to guarantee structural integrity during cycling. To demonstrate its effectiveness, polyanion-type phosphates (e.g., Na3 (VO)2 (PO4 )2 F) and chalcogenides (e.g., MoS2 , VS2 ) are adopted as cathode and anode materials of SIBs, respectively. As compared to traditional binders (e.g., PVDF, SA), electrodes with the SA-GO binder exhibits significantly increased rate capability and cycling stability, such as Na3 (VO)2 (PO4 )2 F (40 C fast-charge, 84% capacity retention after 1000 cycles). This work highlights the role of novel aqueous-based binders in developing next-generation sodium-storage devices.

Ultrastable Graphite-Potassium Anode through Binder Chemistry.

Graphite with abundant reserves has attracted enormous research interest as an anode of potassium-ion batteries (PIBs) owing to its high plateau capacity of 279 mAh g-1 at ≈0.2 V in conventional carbonate electrolytes. Unfortunately, it suffers from fast capacity decay during K+ storage. Herein, an ultrastable graphite-potassium anode is developed through binder chemistry. Polyvinyl alcohol (PVA) is utilized as a water-soluble binder to generate a uniform and robust KF-rich SEI film on the graphite surface, which can not only inhibit the electrolyte decomposition, but also withstand large volume expansion during K+ -insertion. Compared to the PVDF as binder, PVA-based graphite anode can operate for over 2000 cycles (running time of 406 days at C/3) with 97% capacity retention in KPF6 -based electrolytes. The initial Coulombic efficiency (ICE) of graphite anode is as high as 81.6% using PVA as the binder, higher than that of PVDF (40.1%). Benefiting from the strong adhesion ability of PVA, a graphite||fluorophosphate K-ion full battery is further built through 3D printing, which achieves a record-high areal energy of 8.9 mWh cm-2 at a total mass loading of 38 mg cm-2 . These results demonstrate the important role of binder in developing high-performance PIBs.

A Mechanically Flexible Necklace-Like Architecture for Achieving Fast Charging and High Capacity in Advanced Lithium-Ion Capacitors.

Integration of fast charging, high capacity, and mechanical flexibility into one electrode is highly desired for portable energy-storage devices. However, a high charging rate is always accompanied by capacity decay and cycling instability. Here, a necklace-structured composite membrane consisting of micron-sized FeSe2 cubes uniformly threaded by carbon nanofibers (CNF) is reported. This unique electrode configuration can not only accommodate the volumetric expansion of FeSe2 during the lithiation/delithiation processes for structural robustness but also guarantee ultrafast kinetics for Li+ entry. At a high mass loading of 6.2 mg cm-2 , the necklace-like FeSe2 @CNF electrode exhibits exceptional rate capability (80.7% capacity retention from 0.1 to 10 A g-1 ) and long-term cycling stability (no capacity decay after 1100 charge-discharge cycles at 2 A g-1 ). The flexible lithium-ion capacitor (LIC) fabricated by coupling a pre-lithiated FeSe2 @CNF anode with a porous carbon cathode delivers impressive volumetric energy//power densities (98.4 Wh L-1 at 157.1 W L-1 , and 58.9 Wh L-1 at 15714.3 W L-1 ). The top performance, long-term cycling stability, low self-discharge rate, and high mechanical flexibility make it among the best LICs ever reported.

Natural ore molybdenite as a high-capacity and cheap anode material for advanced lithium-ion capacitors.

Hybrid lithium-ion capacitors (LICs) receive special interests because they work by combining the merits of high-capacity lithium-ion batteries and high-rate capacitors in a Li salt containing electrolyte, so as to bridge the gap between the two devices. One of main challenges for LICs is to develop inexpensive and superior anode materials at high rates. In this work, natural molybdenite was utilized as precursor to achieve the scalable production of cheap MoS2/carbon composites. This molybdenite-derived MoS2/carbon electrode can not only exhibit excellent Li+-storage performances including ultrahigh specific capacity (1427 mAh g-1after 1000 cycles at 1 A g-1) and rate capability (554 mAh g-1at 10 A g-1), but also possess four-times higher tap density than that of commercial graphite. By employing MoS2/carbon as the anode and activated carbon as the cathode, the as-assembled LIC device delivers both high energy//high power density and long cycle lifespan. Furthermore, the price is nearly 200 orders of magnitude lower than the traditional high-purity chemicals, which can be easily scaled up to achieve high-throughput production.

Al2 O3 -Assisted Confinement Synthesis of Oxide/Carbon Hollow Composite Nanofibers and Application in Metal-Ion Capacitors.

Hollow micro-/nanostructures are widely explored for energy applications due to their unique structural advantages. The synthesis of hollow structures generally involves a "top-down" casting process based on hard or soft templates. Herein, a new and generic confinement strategy is developed to fabricate composite hollow fibers. A thin and homogeneous atomic-layer-deposition (ALD) Al2 O3 layer is employed to confine the pyrolysis of precursor fibers, which transform into metal (or metal oxide)-carbon composite hollow fibers after removal of Al2 O3 . Because of the uniform coating by ALD, the resultant composite hollow fibers exhibit a hollow interior from heads to ends even if they are millimeter long. V, Fe, Co, and Ni-based hollow nanofibers, demonstrating the versatility of this synthesis method, are successfully synthesized. Because of the carbon constituent, these composite fibers are particularly useful for energy applications. Herein, the as-obtained hollow V2 O3 -C fiber membrane is employed as a freestanding and flexible electrode for lithium-ion capacitor. The device shows an impressive energy density and a high power density.

Dirac Polarons and Resistivity Anomaly in ZrTe_{5} and HfTe_{5}.

Resistivity anomaly, a sharp peak of resistivity at finite temperatures, in the transition-metal pentatellurides ZrTe_{5} and HfTe_{5} was observed four decades ago, and more exotic and anomalous behaviors of electric and thermoelectric transport were revealed in recent years. Here, we present a theory of Dirac polarons, composed by massive Dirac electrons and holes in an encircling cloud of lattice displacements or phonons at finite temperatures. The chemical potential of Dirac polarons sweeps the band gap of the topological band structure by increasing the temperature, leading to the resistivity anomaly. Formation of a nearly neutral state of Dirac polarons accounts for the anomalous behaviors of the electric and thermoelectric resistivity around the peak of resistivity.

Anomalous Temperature Dependence of Quantum Correction to the Conductivity of Magnetic Topological Insulators.

Quantum transport in magnetic topological insulators reveals a strong interplay between magnetism and topology of electronic band structures. A recent experiment on magnetically doped topological insulator Bi_{2}Se_{3} thin films showed the anomalous temperature dependence of the magnetoconductivity while their field dependence presents a clear signature of weak antilocalization [Tkac et al., Phys. Rev. Lett. 123, 036406 (2019)PRLTAO0031-900710.1103/PhysRevLett.123.036406]. Here, we demonstrate that the tiny mass of the surface electrons induced by the bulk magnetization leads to a temperature-dependent correction to the π Berry phase and generates a decoherence mechanism to the phase coherence length of the surface electrons. As a consequence, the quantum correction to conductivity can exhibit nonmonotonic behavior by decreasing the temperature. This effect is attributed to the close relation of the Berry phase and quantum interference of the topological surface electrons in quantum topological materials.

Quantitative Analysis of Weak Antilocalization Effect of Topological Surface States in Topological Insulator BiSbTeSe2.

Quantitative analysis of the weak antilocalization (WAL) effect of topological surface states in topological insulators is of tremendous importance. The major obstacle to achieve accurate results is how to eliminate the contribution of the anisotropic magnetoconductance of bulk states when the Fermi level lies in bulk bands. Here, we demonstrate that we can analyze quantitatively and accurately the WAL effect of topological surface states in topological insulator, BiSbTeSe2 (BSTS), by measuring the anisotropic magnetoconductance. The anomalous conductance peaks induced by the WAL effect of topological surface states of BSTS together with the anisotropic magnetoconductance of bulk states have been observed. By subtracting the anisotropic magnetoconductance of bulk states, we are able to analyze the WAL effect of topological surface states using the Hikami-Larkin-Nagaoka expression. Our findings offer an alternative strategy for the quantitative exploration of the WAL effect of topological surface states in topological insulators.

Large-Area, Uniform, Aligned Arrays of Na3 (VO)2 (PO4 )2 F on Carbon Nanofiber for Quasi-Solid-State Sodium-Ion Hybrid Capacitors.

Sodium-vanadium fluorophosphate (Na3 V2 O2 x (PO4 )2 F3-2 x , NVPF, 0 ≤ x ≤ 1) is considered to be a promising Na-storage cathode material due to its high operation potentials (3.6-4 V) and minor volume variation (1.8%) during Na+ -intercalation. Research about NVPF is mainly focused on powder-type samples, while its ordered array architecture is rarely reported. In this work, large-area and uniform Na3 (VO)2 (PO4 )2 F cuboid arrays are vertically grown on carbon nanofiber (CNF) substrates for the first time. Owing to faster electron/ion transport and larger electrolyte-electrode contact area, the as-prepared NVPF array electrode exhibits much improved Na-storage properties compared to its powder counterpart. Importantly, a quasi-solid-state sodium-ion hybrid capacitor (SIHC) is constructed based on the NVPF array as an intercalative battery cathode and porous CNF as a capacitive supercapacitor anode together with the P(VDF-HFP)-based polymer electrolyte. This novel hybrid system delivers an attractive energy density of ≈227 W h kg-1 (based on total mass of two electrodes), and still remains as high as 107 Wh kg-1 at a high specific power of 4936 W kg-1 , which pushes the energy output of sodium hybrid capacitors toward a new limit. In addition, the growth mechanism of NVPF arrays is investigated in detail.

Mesopore-Induced Ultrafast Na+ -Storage in T-Nb2 O5 /Carbon Nanofiber Films toward Flexible High-Power Na-Ion Capacitors.

Hybrid Na-ion capacitors (NICs) are receiving considerable interest because they combine the merits of both batteries and supercapacitors and because of the low-cost of sodium resources. However, further large-scale deployment of NICs is impeded by the sluggish diffusion of Na+ in the anode. To achieve rapid redox kinetics, herein the controlled fabrication of mesoporous orthorhombic-Nb2 O5 (T-Nb2 O5 )/carbon nanofiber (CNF) networks is demonstrated via in situ SiO2 -etching. The as-obtained mesoporous T-Nb2 O5 (m-Nb2 O5 )/CNF membranes are mechanically flexible without using any additives, binders, or current collectors. The in situ formed mesopores can efficiently increase Na+ -storage performances of the m-Nb2 O5 /CNF electrode, such as excellent rate capability (up to 150 C) and outstanding cyclability (94% retention after 10 000 cycles at 100 C). A flexible NIC device based on the m-Nb2 O5 /CNF anode and the graphene framework (GF)/mesoporous carbon nanofiber (mCNF) cathode, is further constructed, and delivers an ultrahigh power density of 60 kW kg-1 at 55 Wh kg-1 (based on the total weight of m-Nb2 O5 /CNF and GF/mCNF). More importantly, owing to the free-standing flexible electrode configuration, the m-Nb2 O5 /CNF//GF/mCNF NIC exhibits high volumetric energy and power densities (11.2 mWh cm-3 , 5.4 W cm-3 ) based on the full device, which holds great promise in a wide variety of flexible electronics.

Quantum Interference Theory of Magnetoresistance in Dirac Materials.

Magnetoresistance in many samples of Dirac semimetals and topological insulators displays nonmonotonic behavior over a wide range of magnetic fields. Here a formula of magnetoconductivity is presented for massless and massive Dirac fermions in Dirac materials due to quantum interference of Dirac fermions in scalar impurity scattering potentials. It reveals a striking crossover from positive to negative magnetoresistivity, uncovering strong competition between weak localization and weak antilocalization in multiple Cooperon channels at different chemical potentials, effective masses, and finite temperatures. This work sheds light on the important role of strong coupling of the conduction and valence bands in the quantum interference transport in topological nontrivial and trivial Dirac materials.

Co9 S8 /MoS2 Yolk-Shell Spheres for Advanced Li/Na Storage.

Uniform sized Co9 S8 /MoS2 yolk-shell spheres with an average diameter of about 500 nm have been synthesized by a facile route. When evaluated as anodes for lithium-ion and sodium-ion batteries, these Co9 S8 /MoS2 yolk-shell spheres show high specific capacities, excellent rate capabilities, and good cycling stability.

Ultrathin MoSe2@N-doped carbon composite nanospheres for stable Na-ion storage.

Two-dimensional transition metal dichalcogenides are widely studied as anode materials for metal ion batteries. This application requires high electric conductivity which can be achieved by forming composites with conductive carbon. In this work, we demonstrate the creation of nanospheres composed of Mo-based thin nanosheets (MoS2, MoSe2 and Mo2C) uniform embedded within a N-doped carbon matrix. Using MoSe2/N-doped carbon nanospheres as an example, we investigate in detail the electrochemical property in Na ion storage and reveal the advantage over previously reported MoSe2 electrodes (higher capacity and improved capacity retention up to 500 cycles). Furthermore, we provide evidence by ex situ x-ray diffraction to the nominal irreversible conversion reaction during the first discharge.

3D Hierarchical Porous Mo2 C for Efficient Hydrogen Evolution.

Porous electrocatalyst for hydrogen production. 3D hierarchical porous molybdenum carbide provides a low operating potential (97 mV at 10 mA cm(-2) ). These beneficial textures of large specific surface area (302 m(2) g(-1) ) and hierarchical porous architecture containing dominant pore size distribution peak at 11 Å in width can provide large surface active sites and facilitate proton mass transport.

A high energy and power Li-ion capacitor based on a TiO2 nanobelt array anode and a graphene hydrogel cathode.

A novel hybrid Li-ion capacitor (LIC) with high energy and power densities is constructed by combining an electrochemical double layer capacitor type cathode (graphene hydrogels) with a Li-ion battery type anode (TiO(2) nanobelt arrays). The high power source is provided by the graphene hydrogel cathode, which has a 3D porous network structure and high electrical conductivity, and the counter anode is made of free-standing TiO(2) nanobelt arrays (NBA) grown directly on Ti foil without any ancillary materials. Such a subtle designed hybrid Li-ion capacitor allows rapid electron and ion transport in the non-aqueous electrolyte. Within a voltage range of 0.0-3.8 V, a high energy of 82 Wh kg(-1) is achieved at a power density of 570 W kg(-1). Even at an 8.4 s charge/discharge rate, an energy density as high as 21 Wh kg(-1) can be retained. These results demonstrate that the TiO(2) NBA//graphene hydrogel LIC exhibits higher energy density than supercapacitors and better power density than Li-ion batteries, which makes it a promising electrochemical power source.

Attapulgite-intercalated g-C3N4/ZnIn2S4 3D hierarchical Z-scheme heterojunction for boosting photocatalytic hydrogen production.

Construction of hierarchical architecture with suitable band alignment for graphitic carbon nitride (g-C3N4) played a pivotal role in enhancing the efficiency of photocatalysts. In this study, a novel attapulgite-intercalated g-C3N4/ZnIn2S4 nanocomposite material (ZIS/CN/ATP, abbreviated as ZCA) was successfully synthesized using the freeze-drying technique, thermal polymerization, and a simple low-temperature hydrothermal method. Attapulgite (ATP) was intercalated into g-C3N4 to effectively regulate its interlayer structure. The results reveal a substantial enlargement of its internal space, thereby facilitating the provision of additional active sites for improved dispersibility of ZnIn2S4. Notably, the optimized photocatalyst, comprising a mass ratio of ATP, g-C3N4, and ZnIn2S4 at 1:1:2.5 respectively, achieves an outstanding hydrogen evolution rate of 3906.15 µmol g-1h-1, without the need for a Pt co-catalyst. This rate surpasses that of pristine g-C3N4 by a factor of 475 and ZnIn2S4 by a factor of 5, representing a significant improvement in performance. This significant enhancement can be primarily attributed to the higher specific surface area, richer active sites, broadened light response range, and efficient interfacial charge transfer channels of the ZCA composite photocatalyst. Furthermore, the Z-scheme photocatalytic mechanism for the sandwich-like layered structure heterojunction was thoroughly investigated using diverse characterization techniques. This work offers new insights for enhancing photocatalytic performance through the expanded utilization of natural minerals, paving the way for future advancements in this field.

Ultrasensitive monitoring of PCB77 in environmental samples using a visible-driven photoelectrochemical sensing platform coupling with exonuclease I assisted in target recycling.

Due to the urgent need for detecting trace amounts of 3,3',4,4'-tetrachlorobiphenyl (PCB77) in the environment, we have developed an efficient and visible-driven photoelectrochemical (PEC) sensing platform based on carbon quantum dots (CQDs) modified titanium dioxide nanorods (TiO2 NRs), coupling with exonuclease I (Exo I) assisted in target recycling for significant signal amplification. CQDs/TiO2 NRs with high visible-light absorption ability and electron-hole separation efficiency is used as photoactive substrate for anchoring anti-PCB77 aptamer and its complementary DNA (cDNA). With the addition of PCB77, the specific interaction between PCB77 and its aptamer forces aptamer to separate from the electrode surface, resulting in an increase in photocurrent density. Adding Exo I in the test system, a self-catalytic target cycle was motivated, which significantly increased the PEC signal by more than twice, achieving signal amplification. The relationship between the photocurrent density changes and the concentrations of PCB77 are utilized to achieve quantitative detection of PCB77. The designed PEC sensing platform has good analytical performance with a detection limit as low as 0.33 pg L-1, high selectivity and stability. Moreover, the PEC sensor is successfully used to evaluate the content of PBC77 in the environment samples. The established sensing platform provides a simple and efficient method for detecting trace amounts of PCB77 in the environment.

Realizing Efficient Activity and High Conductivity of Perovskite Symmetrical Electrode by Vanadium Doping for CO2 Electrolysis.

Solid oxide electrolysis cells (SOECs) show significant promise in converting CO2 to valuable fuels and chemicals, yet exploiting efficient electrode materials poses a great challenge. Perovskite oxides, known for their stability as SOEC electrodes, require improvements in electrocatalytic activity and conductivity. Herein, vanadium(V) cation is newly introduced into the B-site of Sr2Fe1.5Mo0.5O6-δ perovskite to promote its electrochemical performance. The substitution of variable valence V5+ for Mo6+ along with the creation of oxygen vacancies contribute to improved electronic conductivity and enhanced electrocatalytic activity for CO2 reduction. Notably, the Sr2Fe1.5Mo0.4V0.1O6-δ based symmetrical SOEC achieves a current density of 1.56 A cm-2 at 1.5 V and 800 °C, maintaining outstanding durability over 300 h. Theoretical analysis unveils that V-doping facilitates the formation of oxygen vacancies, resulting in high intrinsic electrocatalytic activity for CO2 reduction. These findings present a viable and facile strategy for advancing electrocatalysts in CO2 conversion technologies.

Functionalized Halloysite Scaffold Controls Sodium Dendrite Growth.

Sodium metal is one of the most promising anodes for the prospective low-cost rechargeable batteries. Nevertheless, the commercialization of Na metal anodes remains restricted by sodium dendrite growth. Herein, halloysite nanotubes (HNTs) were chosen as the insulated scaffolds, and Ag nanoparticles were introduced as sodiophilic sites to achieve uniform sodium deposition from bottom to top under the synergistic effect. Density functional theory (DFT) calculation results demonstrated that the presence of Ag greatly increased the binding energy of sodium on HNTs/Ag (-2.85 eV) vs HNTs (-0.85 eV). Meanwhile, thanks to the opposite charges on the inner and outer surfaces of HNTs, faster Na+ transfer kinetics and selective adsorption of SO3CF3- on the inner surface of HNTs were achieved, thus avoiding the formation of space charge. Accordingly, the coordination between HNTs and Ag afforded a high Coulombic efficiency (about 99.6% at 2 mA cm-2), long lifespan in a symmetric battery (for over 3500 h at 1 mA cm-2), and remarkable cycle stability in Na metal full batteries. This work offers a novel strategy to design a sodiophilic scaffold by nanoclay for dendrite-free Na metal anodes.