Room-Temperature Synthesis of Carbon-Nanotube-Interconnected Amorphous NiFe-Layered Double Hydroxides for Boosting Oxygen Evolution Reaction.

The oxygen evolution reaction (OER) is a key half-reaction in electrocatalytic water splitting. Large-scale water electrolysis is hampered by commercial noble-metal-based OER electrocatalysts owing to their high cost. To address these issues, we present a facile, one-pot, room-temperature co-precipitation approach to quickly synthesize carbon-nanotube-interconnected amorphous NiFe-layered double hydroxides (NiFe-LDH@CNT) as cost-effective, efficient, and stable OER electrocatalysts. The hybrid catalyst NiFe-LDH@CNT delivered outstanding OER activity with a low onset overpotential of 255 mV and a small Tafel slope of 51.36 mV dec-1, as well as outstanding long-term stability. The high catalytic capability of NiFe-LDH@CNT is associated with the synergistic effects of its room-temperature synthesized amorphous structure, bi-metallic modulation, and conductive CNT skeleton. The room-temperature synthesis can not only offer economic feasibility, but can also allow amorphous NiFe-LDH to be obtained without crystalline boundaries, facilitating long-term stability during the OER process. The bi-metallic nature of NiFe-LDH guarantees a modified electronic structure, providing additional catalytic sites. Simultaneously, the highly conductive CNT network fosters a nanoporous structure, facilitating electron transfer and O2 release and enriching catalytic sites. This study introduces an innovative approach to purposefully design nanoarchitecture and easily synthesize amorphous transition-metal-based OER catalysts, ensuring their cost effectiveness, production efficiency, and long-term stability.

Defect-Engineered Mesoporous Undoped Carbon Nanoribbons for Benchmark Oxygen Reduction Reaction.

For large-scale fuel cell applications, it is significant to replace expensive Pt-based oxygen reduction reaction (ORR) electrocatalysts with nonprecious metal- or metal-free carbon-based catalysts with high activity. However, it is still challenging to deeply understand the role of intrinsic defects and the origin of ORR activity in pure nanocarbon. Therefore, a novel self-assembly and a pyrolysis strategy to fabricate defect-rich mesoporous carbon nanoribbons are presented. Due to the effective regulation of nanoarchitecture, a vast number of defective catalytic sites (edge defects and holes) are exposed, which thereby enhances the electron transfer kinetics and catalytic activity. Such undoped nanoribbons display a large half-wave potential of 0.837 V, excellent long-term stability, and exceptional methanol tolerance, surpassing the most undoped ORR catalysts and the commercial Pt/C (20 wt.%) catalyst. Structural characterizations and density functional theory (DFT) calculations confirm that the zigzag edge defects and the armchair pentagon at the hole defect are responsible for outstanding ORR performance.

Freestanding ReS2/Graphene Heterostructures as Binder-Free Anodes for Lithium-Ion Batteries.

It is still challenging to develop anode materials with high capacity and long cycling stability for lithium-ion batteries (LIBs). To address such issues, herein, for the first time, we present a three-dimensional and freestanding ReS2/graphene heterostructure (3DRG) as an anode synthesized via a one-pot hydrothermal method. The hybrid shows a hierarchically sandwich-like, nanoporous, and conductive three-dimensional (3D) network constructed by two-dimensional (2D) ReS2/graphene heterostructural nanosheets, which can be directly utilized as a freestanding and binder-free anode for LIBs. When the current density is 100 mA g-1, the 3DRG anode delivers a high reversible specific capacity of 653 mAh g-1. The 3DRG anode also delivers higher rate capability and cycling stability than the bare ReS2 anode. The markedly boosted electrochemical properties derive from the unique nanoarchitecture, which guarantees massive electrochemical active sites, short channels of lithium-ion diffusion, fast electron/ion transportation, and inhibition of the volume change of ReS2 for LIBs.

Atomic Fe/Zn anchored N, S co-doped nano-porous carbon for boosting oxygen reduction reaction.

Dual-single-atom catalysts are well-known due to their excellent catalytic performance of oxygen reduction reaction (ORR) and the tunable coordination environment of the active sites. However, it is still challengable to finely modulate the electronic states of the metal atoms and facilely fabricate a catalyst with dual-single atoms homogeneously dispersed on conductive skeletons with good mass transport. Herein, atomic FeNx/ZnNx sites anchored N, S co-doped nano-porous carbon plates/nanotubes material (Fe0.10ZnNSC) is rationally prepared via a facile room-temperature reaction and high-temperature pyrolysis. The as-prepared Fe0.10ZnNSC catalyst exhibits a positive onset potential of 0.956 V, an impressive half-wave potential of 0.875 V, excellent long-term durability, and a high methanol resistance, outperforming the benchmark Pt/C. The outstanding ORR performance of Fe0.10ZnNSC is due to its unique nanoarchitecture: a large specific surface area (1092.8 cm2 g-1) and well-developed nanopore structure ensure the high accessibility of active sites; the high conductivity of the carbon matrix guarantees a strong ability to transport electrons to the active sites; and the optimized electronic states of FeNx and ZnNx sites possess good oxygen intermediate adsorption/desorption capacity. This strategy can be extended to design and fabricate other non-precious dual-single-atom ORR catalysts.

Hierarchical Ultrathin Layered GO-ZnO@CeO2 Nanohybrids for Highly Efficient Methylene Blue Dye Degradation.

Highly efficient interfacial contact between components in nanohybrids is a key to achieving great photocatalytic activity in photocatalysts and degradation of organic model pollutants under visible light irradiation. Herein, we report the synthesis of nano-assembly of graphene oxide, zinc oxide and cerium oxide (GO-ZnO@CeO2) nanohybrids constructed by the hydrothermal method and subsequently annealed at 300 °C for 4 h. The unique graphene oxide sheets, which are anchored with semiconducting materials (ZnO and CeO2 nanoparticles), act with a significant role in realizing sufficient interfacial contact in the new GO-ZnO@CeO2 nanohybrids. Consequently, the nano-assembled structure of GO-ZnO@CeO2 exhibits a greater level (96.66%) of MB dye degradation activity than GO-ZnO nanostructures and CeO2 nanoparticles on their own. This is due to the thin layers of GO-ZnO@CeO2 nanohybrids with interfacial contact, suitable band-gap matching and high surface area, preferred for the improvement of photocatalytic performance. Furthermore, this work offers a facile building and cost-effective construction strategy to synthesize the GO-ZnO@CeO2 nanocatalyst for photocatalytic degradation of organic pollutants with long-term stability and higher efficiency.

Metal-Organic Framework-Derived Fe-Doped Ni3Se4/NiSe2 Heterostructure-Embedded Mesoporous Tubes for Boosting Oxygen Evolution Reaction.

It is crucial but challenging to promote sluggish kinetics of oxygen evolution reaction (OER) for water splitting via finely tuning the hierarchical nanoarchitecture and electronic structure of the catalyst. To address such issues, herein we present iron-doped Ni3Se4/NiSe2 heterostructure-embedded metal-organic framework-derived mesoporous tubes (Ni-MOF-Fe-Se-400) realized by an interfacial engineering strategy. Due to the hierarchical nanoarchitecture of conductive two-dimensional nanosheet-constructed MOF-derived mesoporous tubes, coupled with fine tuning of the electronic structure via Fe-doping and interactions between Ni3Se4/NiSe2 heterostructures, the Ni-MOF-Fe-Se-400 catalyst delivers superior OER activity: it requires only a low overpotential of 242 mV to achieve 10 mA cm-2 (Ej=10), surpassing the benchmark RuO2 (Ej=10 = 286 mV) and displays exceptional durability in the chronoamperometric i-t test with a small current decay (6.2%) after 72 h. Furthermore, the water splitting system comprises a Ni-MOF-Fe-Se-400 anode and a Pt/C cathode requires a low cell voltage of 1.576 V to achieve Ej=10 with an excellent Faradic efficiency (∼100%), outperforming the RuO2-Pt/C combination. This work presents a novel interfacial engineering strategy to finely adjust the morphology and electronic structure of the non-noble metal-based OER catalyst via a facile fabrication method.

NiFeMn-Layered Double Hydroxides Linked by Graphene as High-Performance Electrocatalysts for Oxygen Evolution Reaction.

Currently, precious metal group materials are known as the efficient and widely used oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalysts. The exorbitant prices and scarcity of the precious metals have stimulated scale exploration of alternative non-precious metal catalysts with low-cost and high performance. Layered double hydroxides (LDHs) are a promising precursor to prepare cost-effective and high-performance catalysts because they possess abundant micropores and nitrogen self-doping after pyrolysis, which can accelerate the electron transfer and serve as active sites for efficient OER. Herein, we developed a new highly active NiFeMn-layered double hydroxide (NFM LDH) based electrocatalyst for OER. Through building NFM hydroxide/oxyhydroxide heterojunction and incorporation of conductive graphene, the prepared NFM LDH-based electrocatalyst delivers a low overpotential of 338 mV at current density of 10 mA cm-2 with a small Tafel slope of 67 mV dec-1, which are superior to those of commercial RuO2 catalyst for OER. The LDH/OOH heterojunction involves strong interfacial coupling, which modulates the local electronic environment and boosts the kinetics of charge transfer. In addition, the high valence Fe3+ and Mn3+ species formed after NaOH treatment provide more active sites and promote the Ni2+ to higher oxidation states during the O2 evolution. Moreover, graphene contributes a lot to the reduction of charge transfer resistance. The combining effects have greatly enhanced the catalytic ability for OER, demonstrating that the synthesized NFM LDH/OOH heterojunction with graphene linkage can be practically applied as a high-performance electrocatalyst for oxygen production via water splitting.

Converting inert AlOOH into efficient electrocatalyst for oxygen evolution reaction via structural/electronic modulation.

Efficient and stable water-splitting electrocatalysts play a key role to obtain green and clean hydrogen energy. However, only a few kinds of materials display an intrinsically good performance towards water splitting. It is significant but challengeable to effectively improve the catalytic activity of inert or less active catalysts for water splitting. Herein, we present a structural/electronic modulation strategy to convert inert AlOOH nanorods into catalytic nanosheets for oxygen evolution reaction (OER) via ball milling, plasma etching and Co doping. Compared to inert AlOOH, the modulated AlOOH delivers much better OER performance with a low overpotential of 400 mV at 10 mA cm-2 and a very low Tafel slope of 52 mV dec-1, even lower than commercial OER catalyst RuO2. Significant performance enhancement is attributed to the electronic and structural modulation. The electronic structure is effectively improved by Co doping, ball milling-induced shear strain, plasma etching-caused rich vacancies; abrupt morphology/microstructure change from nanorod to nanoparticle to nanosheet, as well as rich defects caused by ball milling and plasma etching, can significantly increase active sites; the free energy change of the potential determining step of modulated AlOOH decreases from 2.93 eV to 1.70 eV, suggesting a smaller overpotential is needed to drive the OER processes. This strategy can be extended to improve the electrocatalytic performance for other materials with inert or less catalytic activity.

Dual Fe, Zn single atoms anchored on carbon nanotubes inlaid N, S-doped hollow carbon polyhedrons for boosting oxygen reduction reaction.

It is still challengeable but significant to rationally develop dual-metal single-atom catalysts with rich accessible active sites and excellent intrinsic catalytic activity towards oxygen reduction reaction (ORR). Herein, we present a novel dual-metal single-atom catalyst, Fe and Zn single atoms homogenously anchored on carbon nanotubes inlaid N, S-doped hollow carbon polyhedrons (FeZn-NSC), synthesized by facile iron-salt impregnation and high-temperature pyrolysis for zeolitic imidazolate framework-8. Due to the synergistic effects of the hierarchical porous nanoarchitecture with high specific surface area (795.48 m2 g-1), N, S co-doped hollow carbon polyhedrons, in-situ grown highly conductive carbon nanotubes, and high loading of dual-metal single-atoms of Fe (3.12 wt%) and Zn (3.71 wt%), the optimized FeZn-NSC delivers outstanding ORR performance with high half-wave potential of 0.87 V, low Tafel slope of 44.7 mV dec-1, long-term durability, and strong tolerance of methanol crossover. This work provides a strategy to rationally design and facilely synthesize dual-metal single-atom catalysts with high ORR activity.

In Situ Construction of Bronze/Anatase TiO2 Homogeneous Heterojunctions and Their Photocatalytic Performances.

Photocatalytic degradation is one of the most promising emerging technologies for environmental pollution control. However, the preparation of efficient, low-cost photocatalysts still faces many challenges. TiO2 is a widely available and inexpensive photocatalyst material, but improving its catalytic degradation performance has posed a significant challenge due to its shortcomings, such as the easy recombination of its photogenerated electron-hole pairs and its difficulty in absorbing visible light. The construction of homogeneous heterojunctions is an effective means to enhance the photocatalytic performances of photocatalysts. In this study, a TiO2(B)/TiO2(A) homogeneous heterojunction composite photocatalyst (with B and A denoting bronze and anatase phases, respectively) was successfully constructed in situ. Although the construction of homogeneous heterojunctions did not improve the light absorption performance of the material, its photocatalytic degradation performance was substantially enhanced. This was due to the suppression of the recombination of photogenerated electron-hole pairs and the enhancement of the carrier mobility. The photocatalytic ability of the TiO2(B)/TiO2(A) homogeneous heterojunction composite photocatalyst was up to three times higher than that of raw TiO2 (pure anatase TiO2).

Template free-synthesis of cobalt-iron chalcogenides [Co0.8Fe0.2L2, L = S, Se] and their robust bifunctional electrocatalysis for the water splitting reaction and Cr(vi) reduction.

The ease of production of materials and showing multiple applications are appealing in this modern era of advanced technology. This paper reports the synthesis of a pair of novel cobalt-iron chalcogenides [Co0.8Fe0.2S2 and Co0.8Fe0.2Se2] with enhanced electro catalytic activities. These ternary metal chalcogenides were synthesized by a one-step template-free approach via a hexamethyldisilazane (HMDS)-assisted synthetic method. Transient photocurrent (TPC) studies and electrochemical impedance spectra (EIS) of these materials showed free electron mobility. Their bifunctional activities were verified in both the electrochemical oxygen evolution reaction (OER) and in the electrochemical reduction of toxic inorganic heavy metal ions [Cr(vi)] in polluted water. The materials showed robust catalytic ability in the oxygen evolution reaction with minimum possible over potential (345 and 350 mV @ η10) as determined by linear sweep voltammetry and the lower Tafel values (52.4 and 84.5 mV dec-1) for Co0.8Fe0.2Se2 and Co0.8Fe0.2S2 respectively. Surprisingly, both the materials also showed an excellent activity towards electrochemical Cr(vi) reduction to Cr(iii). Besides the maximum current achieved for Co0.8Fe0.2S2, a minimum value for the Limit of detection (LOD) was obtained for Co0.8Fe0.2S2 (0.159 µg L-1) compared to Co0.8Fe0.2Se2 (0.196 µg L-1). We tested the durability of catalysts, the critical factor for the prolonged use of catalysts, through the recyclability measurements of these materials as catalysts. Both the catalysts presented outstanding durability and balanced electro catalytic activities for up to 1500 CV cycles, and chronoamperometry studies also confirmed exceptional stability. The enhanced catalytic activities of these materials are ascribed to the free electron movement, evidenced by the increased TPC measured and EIS. Therefore, the template-free synthesis of these electro catalysts containing non-noble metal illustrates the practical approach to develop such types of catalysts for multiple functions.

Lithiophilic Mo3N2/MoN as multifunctional interlayer for dendrite-free and ultra-stable lithium metal batteries.

The formation of lithium dendrite and the unstable electrode/electrolyte interface, especially at high rates, are the dominant obstacles impeding the implementation of lithium metal batteries (LMBs). To tackle these fundamental challenges, here we propose a lithiophilic Mo3N2/MoN heterostructure (designated as MoNx) interlayer for dendrite-free and ultra-stable lithium metal anodes for the first time. The MoNx interlayer presents excellent electrolyte wettability, fast lithium diffusion kinetics and strong mechanical strength, which function synergistically to inhibit lithium dendrite growth. During cycling, an in-situ formation of Li3N-rich solid electrolyte interphase layer and metallic Mo phase can regulate the Li-ion conductivity and Li metal deposition, thus indicating uniform and compact Li plating. Above ameliorating features accompany an ultra-long-life of 2000 h at a high current density of 5 mA cm-2 for the MoNx-Li anode. The feasibility of the MoNx-Li anode in LMB is further confirmed in conjunction with LiFePO4 cathodes. The full cells deliver exceptionally high-capacity retentions of above 82.0% after 500 cycles at 1C and 425 cycles at 3C, which are among the best thus far reported for LMBs. This work provides both new insights towards functional interlayer design and effective transition-metal nitrides for practical LMBs.

Rationally Designed Ag@polymer@2-D LDH Nanoflakes for Bifunctional Efficient Electrochemical Sensing of 4-Nitrophenol and Water Oxidation Reaction.

The rational design and demonstration of a facile sequential template-mediated strategy to construct noble-metal-free efficient bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and electrocatalytic detection of hazardous environmental 4-nitrophenol (4-NP) have continued as a major challenging task. Herein, we construct a novel Ag@polymer/NiAl LDH (designated as APL) nanohybrid as an efficient bifunctional electrocatalyst by a simple hydrolysis method. The well-fabricated APL/GCE exhibited an extensive linear range from 0.1 to 100 µM in optimized conditions. It showed a detection limit (LOD) of 0.0096 µM (9.6 nM) (S/N = 3) for 4-NP in pH 6 by differential pulse voltammetry (DPV). Meanwhile, the newly fabricated APL exhibited outstanding OER activity with a very low overpotential of 259 mV to deliver 10 mA cm-2 current density (J) at a scan rate of 5 mV/s. The Tafel plot value of APL is low (97 mV/dec) compared to that of the benchmark RuO2 due to a fast kinetic reaction. Besides, the durability of the electrocatalyst was assessed by a chronoamperometry test (CA) for 36 h at 1.55 mV vs RHE, and the long-term cycling stability was analyzed by using cyclic voltammetry (CV); after 5000 cycles, the electrocatalyst was highly stable. These demonstrated results could lead to an alternative electrocatalyst construction for the bifunctionally efficient electrochemical sensing of 4-nitrophenol and oxygen evolution reaction.

Three-dimensional porous MoS2 nanobox embedded g-C3N4@TiO2 architecture for highly efficient photocatalytic degradation of organic pollutant.

Herein, a simple, highly efficient and stable MoS2 nanobox embedded graphitic-C3N4@TiO2 (g-CN@TiO2) nanoarchitecture was synthesized by a facile solvothermal approach. The nano-hybrid photocatalyst was constructed by TiO2 nanoparticles anchored on the surface of g-CN nanosheets. Then highly crystalline three-dimensional porous MoS2 nanobox was homogeneously distributed on the g-CN@TiO2 surface. The g-CN@TiO2/MoS2 hybrid achieved a high photocatalytic degradation efficiency of 97.5% for methylene blue (MB) dye pollutant under visible-light irradiant in an hour which was much better than TiO2@MoS2, g-CN@TiO2, MoS2, TiO2 and g-CN. Furthermore, the reaction rate (k) value of g-CN@TiO2/MoS2 for MB dye is as high as 3.18 X 10-2 min-1, which is ~ 2.65 times better than those of g-CN@TiO2 and MoS2. This work presents a rational structure design, interfacial construction and suitable band gap strategy to synthesize advanced nano-hybrid photocatalyst for degradation of organic pollutant with excellent performance and long-term stability.

Outstanding Catalytic Effects of 1T'-MoTe2 Quantum Dots@3D Graphene in Shuttle-Free Li-S Batteries.

It is still challenging to develop sulfur electrodes for Li-S batteries with high electrical conductivity and fast kinetics, as well as efficient suppression of the shuttling effect of lithium polysulfides. To address such issues, herein, polar MoTe2 with different phases (2H, 1T, and 1T') were deeply investigated by density functional theory calculations, suggesting that the 1T'-MoTe2 displays concentrated density of states (DOS) near the Fermi level with high conductivity. By optimization of the synthesis, 1T'-MoTe2 quantum dots decorated three-dimensional graphene (MTQ@3DG) was prepared to overcome these issues, and it accomplished exceptional performance in Li-S batteries. Owing to the chemisorption and high catalytic effect of 1T'-MoTe2 quantum dots, MTQ@3DG/S exhibits highly reversible discharge capacity of 1310.1 mAh g-1 at 0.2 C with 0.026% capacity fade rate per cycle over 600 cycles. The adsorption calculation demonstrates that the conversion of Li2S2 to Li2S is the rate-limiting step where the Gibbs free energies are 1.07 eV for graphene and 0.97 eV for 1T'-MoTe2, revealing the importance of 1T'-MoTe2. Furthermore, in situ Raman spectroscopy investigation proved the suppression of the shuttle effect of LiPSs in MTQ@3DG/S cells during the cycle.

Fabrication of Highly Textured 2D SnSe Layers with Tunable Electronic Properties for Hydrogen Evolution.

Hydrogen is regarded to be one of the most promising renewable and clean energy sources. Finding a highly efficient and cost-effective catalyst to generate hydrogen via water splitting has become a research hotspot. Two-dimensional materials with exotic structural and electronic properties have been considered as economical alternatives. In this work, 2D SnSe films with high quality of crystallinity were grown on a mica substrate via molecular beam epitaxy. The electronic property of the prepared SnSe thin films can be easily and accurately tuned in situ by three orders of magnitude through the controllable compensation of Sn atoms. The prepared film normally exhibited p-type conduction due to the deficiency of Sn in the film during its growth. First-principle calculations explained that Sn vacancies can introduce additional reactive sites for the hydrogen evolution reaction (HER) and enhance the HER performance by accelerating electron migration and promoting continuous hydrogen generation, which was mirrored by the reduced Gibbs free energy by a factor of 2.3 as compared with the pure SnSe film. The results pave the way for synthesized 2D SnSe thin films in the applications of hydrogen production.

Hollow CoP/FeP4 Heterostructural Nanorods Interwoven by CNT as a Highly Efficient Electrocatalyst for Oxygen Evolution Reactions.

Electrolysis of water to produce hydrogen is crucial for developing sustainable clean energy and protecting the environment. However, because of the multi-electron transfer in the oxygen evolution reaction (OER) process, the kinetics of the reaction is seriously hindered. To address this issue, we designed and synthesized hollow CoP/FeP4 heterostructural nanorods interwoven by carbon nanotubes (CoP/FeP4@CNT) via a hydrothermal reaction and a phosphorization process. The CoP/FeP4@CNT hybrid catalyst delivers prominent OER electrochemical performances: it displays a substantially smaller Tafel slope of 48.0 mV dec-1 and a lower overpotential of 301 mV at 10 mA cm-2, compared with an RuO2 commercial catalyst; it also shows good stability over 20 h. The outstanding OER property is mainly attributed to the synergistic coupling between its unique CNT-interwoven hollow nanorod structure and the CoP/FeP4 heterojunction, which can not only guarantee high conductivity and rich active sites, but also greatly facilitate the electron transfer, ion diffusion, and O2 gas release and significantly enhance its electrocatalytic activity. This work offers a facile method to develop transition metal-based phosphide heterostructure electrocatalysts with a unique hierarchical nanostructure for high performance water oxidation.

Self-assembled CoSe2-FeSe2 heteronanoparticles along the carbon nanotube network for boosted oxygen evolution reaction.

Water electrolysis is a significant alternative technique to produce clean hydrogen fuel in order to replace environmentally destructive fossil fuel combustion. However, the sluggish oxygen evolution kinetics makes this process vulnerable as it requires relatively high overpotentials. Hence, significantly effective electrocatalysts are necessary to access the water-oxidation process at a low overpotential to make this process industrially viable. Therefore, in order to reduce the energy barrier, we developed bimetallic CoSe2-FeSe2 heteronanoparticles along the carbon nanotube network (CoSe2-FeSe2/CNT) via a facile selenization strategy. Due to the unique assembly of highly conductive nanoparticles along the CNT network, the CoSe2-FeSe2/CNT displays an exceptionally good oxygen evolution (OER) activity; it requires 248 mV overpotential to reach a current density of 10 mA cm-2 (η10) with an ultra-low Tafel slope of 36 mV dec-1 and displays an overpotential of 1.59 V (η10) in the full water-splitting catalysis with the commercial Pt/C cathode. The high OER activity of CoSe2-FeSe2/CNT over the monometallic CoSe2/CNT and FeSe2/CNT electrocatalysts approve the synergistic interactions. Therefore, the superior performance is possibly ascribed to the unique porous nanoarchitecture and the strong coupling interactions between CoSe2 and FeSe2 heteronanoparticles on the conductive network. This study introduces an innovative approach to rationally design and fabricate cost-effective and highly proficient electrocatalysts for boosted OER performance.

Lithiophilic 3D VN@N-rGO as a Multifunctional Interlayer for Dendrite-Free and Ultrastable Lithium-Metal Batteries.

It is still a big challenge to effectively suppress dendrite growth, which increases the safety and life of lithium-metal-based high energy/power density batteries. To address such issues, herein we design and fabricate a lithiophilic VN@N-rGO as a multifunctional layer on commercial polypropylene (PP) separator, which is constructed by a thin N-rGO nanosheet-wrapped VN nanosphere with a uniform pore distribution, relatively high lithium ionic conductivity, excellent electrolyte wettability, additional lithium-ion diffusion pathways, high mechanical strength, and reliable thermal stability, which are beneficial to regulate the interfacial lithium ionic flux, resulting in the formation of a stable and homogeneous current density distribution on Li-metal electrodes and hard modified separators that can resist dendrites piercing. Consequently, the growth of Li dendrite is effectively suppressed, and the cycle stability of lithium-metal batteries is significantly improved. In addition, even at a high current density of 10 mA cm-2 and cutoff areal capacity of 5 mAh cm-2, the Li|Li symmetric batteries with VN@N-rGO/PP separators still work very well even over 2500 h, exhibiting ultrahigh cycling stability. This work presents rational design ideas and a facile fabrication strategy of a lithiophilic 3D porous multifunctional interlayer for dendrite-free and ultrastable lithium-metal-based batteries.

In Situ Construction of Mo2 C Quantum Dots-Decorated CNT Networks as a Multifunctional Electrocatalyst for Advanced Lithium-Sulfur Batteries.

The slow redox kinetics during cycling process and the serious shuttle effect caused by the solubility of lithium polysulfides (LiPSs) dramatically hinder the practical application of Li-S batteries. Herein, a facile and scalable spray-drying strategy is presented to construct conductive polar Mo2 C quantum dots-decorated carbon nanotube (CNT) networks (MCN) as an efficient absorbent and electrocatalyst for Li-S batteries. The results reveal that the MCN/S electrode exhibits a high specific capacity of 1303.3 mAh g-1 at 0.2 C, and ultrastable cycling stability with decay of 0.019% per cycle even at 1 C. Theoretical simulation uncovers that Mo2 C exhibits much stronger binding energies for S8 and Li2 Sn . The energy barrier for the conversion between Li2 S4 and Li2 S2 decreases from 1.02 to 0.72 eV when hybriding with Mo2 C. Furthermore, in situ discharge/charge-dependent Raman spectroscopy shows that long-chain Li2 S8 configuration is generated via S8 ring opening near the first plateaus at ≈2.36 V versus Li/Li+ and the S6 2- configuration in CNT/S electrode is maintained below the potential of ≈2.30 V versus Li/Li+ , indicating that the shuttle of soluble LiPSs happens during the whole discharge process. This work provides deep insights into the polar nanoarchitecture design and scalable fabrication for advanced Li-S batteries.