Revealing the key role of non-solvating diluents for fast-charging and low temperature Li-ion batteries

Fast-charging and low temperature operation are of vital importance for the further development of lithium-ion batteries(LIBs),which is hindered by the utilization of conventional carbonate-based electrolytes due to their slow kinetics,narrow operating temperature and voltage range.Herein,an acetonitrile(AN)-based localized high-concentration electrolyte(LHCE)is proposed to retain liquid state and high ionic conductivity at ultra-low temperatures while possessing high oxidation stability.We originally reveal the excellent thermal shielding effect of non-solvating diluent to prevent the aggregation of Li^(+) solvates as temperature drops,maintaining the merits of fast Li transport and facile desolvation as at room temperature,which bestows the graphite electrode with remarkable low temperature performance(264 mA h g^(-1) at-20 C).Remarkably,an extremely high capacity retention of 97%is achieved for high-voltage high-energy graphite||NCM batteries after 250 cycles at-20 C,and a high capacity of 110 mA h g^(-1)(71%of its room-temperature capacity)is retained at-30°C.The study unveils the key role of the non-solvating diluents and provides instructive guidance in designing electrolytes towards fast-charging and low temperature LIBs.

Tailored deep-eutectic solvent method to enable 3D porous iron fluoride bricks for conversion-type lithium batteries

Conversion-type fluoride cathode can provide considerable energy density for Li batteries,however its scalable and facile synthesis strategies are still lacking.Here,a novel Fe-based deep eutectic solvent composed of nitrite and methylsulfonylmethane is proposed as both the reaction medium and precursor to synthesize O-doped FeF3porous bricks.This method is cheaper,safe,mildly operable,environmentally friendly and recyclable for non-fluorinated metal cations.The homogenization of charge and mass transport in cathode network effectively mitigates the volume extrusion and electrode coarsening even for the micro-sized monolithic particles.The Co-solvation modulated fluoride cathode delivers high reversible capacity in a wide temperature range(486 and 235 mA h g^(-1)at 25℃ and-20℃ respectively),excellent rate performance(312 mA h g^(-1)at 1000 mA g^(-1)),corresponding to an energy density as high as672.1 W h kg^(-1)under a power density of 2154.3 W kg^(-1).The successful operation of fluoride pouchcell with a capacity exceeding 450 mA h g^(-1)(even under thin Li foil and lean electrolyte conditions) indicates its potentiality of commercial application.

Oriented Organization of Poly(3-Hexylthiophene)for Efficient and Stable Antimony Sulfide Solar Cells

Poly(3-hexylthiophene)(P3HT),as a traditional organic hole-transporting material(HTM),is widely used in thin-film solar cells due to its high charge mobility and good thermal stability.However,the P3HT films obtained by the traditional method are amorphous,which is unfavorable to hole extraction and transport.Here,a low-toxicity solvent 1,2,4-trimethylbenzene(TMB)was used as the solvent instead of the commonly used halogen solvent chlorobenzene(CB)to dissolve P3HT.Thus,the self-assembled nanofibrous P3HT film was prepared and applied as HTM in the newly emerged Sb_(2)S_(3)solar cells.According to the density functional theory calculations,the interface contact between TMB-P3HT and Sb_(2)S_(3)was enhanced via the bonding interaction of S in P3HT and Sb in Sb_(2)S_(3).Through transient absorption spectroscopy characterization,the enhanced interface contact improves the charge extraction ability of TMB-P3HT when compared to the CB-P3HT film.Thus,the TMB-P3HT-based Sb_(2)S_(3)solar cell delivers a power conversion efficiency of 6.21%,which is 9.7%higher than that of the CB-P3HT-based device.Furthermore,the dopant-free TMB-P3HT-based Sb_(2)S_(3)devices exhibit excellent environmental stability compared with Spiro-OMeTAD-based devices.This work demonstrates that the application of P3HT and the solvent engineering of HTM are applicable strategies for developing Sb_(2)S_(3)solar cells with high efficiency and stability.

Trimetallic Metal-Organic Framework Nanoframe Superstructures: A Stress-Buffering Architecture Engineering of Anode Material toward Boosted Lithium Storage Performance

Metal-organic frameworks(MOFs)can serve as prevailing anodes for lithium-ion batteries,due to their multiple redox-active sites and prominent structural compatibility.However,the poor electronic conductivity and inferior cyclability hinder their further implementation.Herein,a synthetic methodology for trimetallic Fe-Co-Ni MOFs with nanoframe superstructures architecture(Fe-Co-Ni NFSs)via structural evolution is proposed for versatile anode materials for lithium storage.Ascribed to optimal compositional and structural optimization,the Fe-Co-Ni NFSs achieve exceptional electrochemical performance with superior specific capacity(1030 mAh g^(−1) at 0.1 A g^(−1)),outstanding rate capacity(414 mAh g^(−1) at 2 A g^(−1)),and prolonged cyclability(489 mAh g^(−1) upon 1000 cycles at 1 A g^(−1)).Both experimental and theoretical investigations reveal that the multi-component metal centers could boost electronic conductivity,confer multiple active sites,and energetically favor Li adsorption capability.Additionally,the nanoframe superstructures of Fe-Co-Ni NFSs could facilitate stress-buffering effect on volumetric expansion and prevent electrode pulverization,further improving the lithium storage capability.This work envisions a meticulous protocol for high-performance MOF anode materials for lithium-ion batteries.

Advances in in-situ characterizations of electrode materials for better supercapacitors

In past decades,the performance of supercapacitors has been greatly improved by rationalizing the electrode materials at the nanoscale.However,there is still a lack of understanding on how the charges are efficiently stored in the electrodes or transported across the electrolyte/electrode interface.As it is very challenging to investigate the ion-involved physical and chemical processes with single experiment or computation,combining advanced analytic techniques with electrochemical measurements,i.e.,developing in-situ characterizations,have shown considerable prospect for the better understanding of behaviors of ions in electrodes for supercapacitors.Herein,we briefly review several typical in-situ techniques and the mechanisms these techniques reveal in charge storage mechanisms specifically in supercapacitors.Possible strategies for designing better electrode materials are also discussed.

Overcoming the Na-ion conductivity bottleneck for the cost-competitive chloride solid electrolytes

Chloride solid electrolytes possess multiple advantages for the construction of safe,energy-dense allsolid-state sodium batteries,but presently the chlorides with sufficiently high cost-competitiveness for commercialization almost all exhibit low Na-ion conductivities of around 10^(-5)S cm^(-1)or lower.Here,we report a chloride solid electrolyte,Na_(2.7)ZFCl_(5.3)O_(0.7),which reaches a Na-ion conductivity of 2.29×10^(-4)S cm^(-1)at 25℃without involving overly expensive raw materials such as rare-earth chlorides or Na_(2)S.In addition to the efficient ion transport,Na_(2.7)ZrCl_(5.3)O_(0.7)also shows an excellent deformability surpassing that of the widely studied Na_(3)PS_(4),Na_(3)SbS_(4),and Na_(2)ZrCl_(6)solid electrolytes.The combination of these advantages allows the all-solid-state cell based on Na_(2.7)ZrCl_(5.3)O_(0.7)and NaCrO_(2)to realize stable room-temperature cycling at a much higher specific current than those based on other non-viscoelastic chloride solid electrolytes in literature(120 mA g^(-1)vs.12-55 mA g^(-1));after 100 cycles at such a high rate,the Na_(2.7)ZFCl_(5.3)O_(0.7)-based cell can still deliver a discharge capacity of 80 mAh g^(-1)at25℃.

Stabilizing perovskite precursors with the reductive natural amino acid for printable mesoscopic perovskite solar cells

Solution processability significantly advances the development of highly-efficient perovskite solar cells.However,the precursor solution tends to undergo irreversible degradation reactions,impairing the device performance and reproducibility.Here,we utilize a reductive natural amino acid,Nacetylcysteine(NALC),to stabilize the precursor solution for printable carbon-based hole-conductorfree mesoscopic perovskite solar cells.We find that I_(2) can be generated in the aged solution containing methylammonium iodide(MI) in an inert atmosphere and speed up the MA-FA^(+)(formamidinium) reaction which produces large-size cations and hinders the formation of perovskite phase.NALC effectively stabilizes the precursor via its sulfhydryl group which reduces I_(2) back to I^(-)and provides H^(+).The NALC-stabilized precursor which is aged for 1440 h leads to devices with a power conversion efficiency equivalent to 98% of that for devices prepared with the fresh precursor.Furthermore,NALC improves the device power conversion efficiency from 16.16% to 18.41% along with enhanced stability under atmospheric conditions by modifying grain boundaries in perovskite films and reducing associated defects.

Tailored multifunctional hydrazine derivatives for efficient printable hole-conductive-free mesoscopic perovskite solar cells via enhancing defect passivation

The low-cost and easy large-scale fabrication advantages of printable mesoscopic perovskite solar cells(p-MPSCs)are overshadowed by their limited photovoltaic conversion efficiency(PCE).Here,we introduce the hydrazide derivative of 4-Hydroxybenzoylhydrazine(4-HBH)to improve the PCE of p-MPSCs by inducing enhanced defect passivation.Both carbonyl and hydrazine groups in hydrazide groups present strong interaction with perovskite.The hydroxyl group,as an electron donor group,increases the electron cloud density of the hydrazide group in 4-HBH under the conjugation of the benzene ring,and thus enhances its interaction with perovskite.Additionally,the hydroxy group itself interacts with perovskite and passivates defects synergistically.The hydrazine agents can also reduce I2and suppress the loss of iodine in perovskite films,which inhibits the formation of iodine-related defects.Consequently,p-MPSCs with 4-HBH achieve a high PCE of 19.21%,and present well improved stability.

Highly efficient and selective photocatalytic dehydrogenation of benzyl alcohol for simultaneous hydrogen and benzaldehyde production over Ni-decorated Zn_(0.5)Cd_(0.5)S solid solution

Photocatalytic conversion of solar energy into hydrogen and high value-added fine chemicals has attracted increasing attention. Herein, we demonstrate an efficient photocatalytic system for simultaneous hydrogen evolution and benzaldehyde production by dehydrogenation of benzyl alcohol over Nidecorated Zn_(0.5)Cd_(0.5)S solid solution under visible light. The photocatalytic system shows an excellent hydrogen production rate of 666.3 μmol h^(-1) with high stability. The optimal apparent quantum yield of52.5% is obtained at 420 nm. This noble-metal-free photocatalytic system displays much higher activity than pure Zn_(0.5)Cd_(0.5)S and Pt-loaded Zn_(0.5)Cd_(0.5)S solid solution. Further studies reveal that the metallic Ni nanocrystals play an important role in accelerating the separation of photogenerated charge carriers and the subsequent cleavage of α-C–H bond during dehydrogenation of benzyl alcohol.

Preparation of dense Ta-LLZO/MgO composite Li-ion solid electrolyte:Sintering, microstructure, performance and the role of MgO

Cubic phase Li7La3Zr2O12(LLZO),a member of the Li–Garnet family,is a promising solid electrolyte and has been widely studied in recent years.However,LLZO samples prepared via conventional ambient air sintering reported in the published literature often contain large grains with lower than desired(<94%)relative density.In this study,a non-contact method of co-firing with mother powder method is proposed to prepare high-quality Ta-doped LLZO–MgO composite ceramics.By sintering at 1150℃for 5 h,the ceramics can reach relative density of 98.2%,conductivity of 5.17×10^-4 S cm^-1 at 25℃and fracture strength of 150 MPa.The sintered samples have uniform fine-grained microstructure and high critical current densities of 0.75–0.95 mA cm-2 at room temperature in Li–Li symmetry cell with Au modification.In addition,systematic sintering experiments and characterizations are conducted to explore the function of MgO in inhibiting the Ta-LLZO grain growth and its existing form inside the composite ceramics.

Carbon materials for stable Li metal anodes: Challenges, solutions, and outlook

Lithium(Li)metal is regarded as the ultimate anode for next-generation Li-ion batteries due to its highest specific capacity and lowest electrochemical potential.However,the Li metal anode has limitations,including virtually infinite volume change,nonuniform Li deposition,and an unstable electrode-electrolyte interface,which lead to rapid capacity degradation and poor cycling stability,significantly hindering its practical application.To address these issues,intensive efforts have been devoted toward accommodating and guiding Li deposition as well as stabilizing the interface using various carbon materials,which have demonstrated excellent effectiveness,benefiting from their vast variety and excellent tunability of the structure-property relationship.This review is intended as a guide through the fundamental challenges of Li metal anodes to the corresponding solutions utilizing carbon materials.The specific functionalities and mechanisms of carbon materials for stabilizing Li metal anodes in these solutions are discussed in detail.Apart from the stabilization of the Li metal anode in liquid electrolytes,attention has also been paid to the review of anode-free Li metal batteries and solid-state batteries enabled by strategies based on carbon materials.Furthermore,we have reviewed the unresolved challenges and presented our outlook on the implementation of carbon materials for stabilizing Li metal anodes in practical applications.

Nitrate-group-grafting-induced assembly of rutile TiO2 nanobundles for enhanced photocatalytic hydrogen evolution

In this study,an acid-induced assembly strategy for a rutile TiO2 photocatalyst was proposed on the basis of the treatment of lamellar protonated titanate with a concentrated HNO3 solution.Nitrate groups were successfully grafted onto a TiO2 surface and induced the assembly of rutile TiO2 nanorods into uniform spindle-like nanobundles.The resulting TiO2 product achieved a photocatalytic hydrogen evolution rate of 402.4μmol h^?1,which is 3.1 times higher than that of Degussa P25-TiO2.It was demonstrated that nitrate group grafting caused the rutile TiO2 surface to become negatively charged,which is favorable for trapping positive protons and improving charge carrier separation,thereby enhancing photocatalytic hydrogen production.Additionally,surface charges were crucial to structural stability based on electrostatic repulsion.This study not only developed a facile surface modification strategy for fabricating efficient H2 production photocatalysts but also identified an influence mechanism of inorganic acids different from that reported in the literature.

Recent Advances on MOF Derivatives for Non-Noble Metal Oxygen Electrocatalysts in Zinc-Air Batteries

Oxygen electrocatalysts are of great importance for the air electrode in zinc-air batteries(ZABs).Owing to the high specific surface area,controllable pore size and unsaturated metal active sites,metal-organic frameworks(MOFs)derivatives have been widely studied as oxygen electrocatalysts in ZABs.To date,many strategies have been developed to generate efficient oxygen electrocatalysts from MOFs for improving the performance of ZABs.In this review,the latest progress of the MOF-derived non-noble metal-oxygen electrocatalysts in ZABs is reviewed.The performance of these MOF-derived catalysts toward oxygen reduction,and oxygen evolution reactions is discussed based on the categories of metal-free carbon materials,single-atom catalysts,metal cluster/carbon composites and metal compound/carbon composites.Moreover,we provide a comprehensive overview on the design strategies of various MOF-derived non-noble metal-oxygen electrocatalysts and their structure-performance relationship.Finally,the challenges and perspectives are provided for further advancing the MOF-derived oxygen electrocatalysts in ZABs.

Enhanced Pseudo‑Capacitive Contributions to High‑Performance Sodium Storage in TiO2/C Nanofibers via Double Effects of Sulfur Modification

Pseudo-capacitive mechanisms can provide higher energy densities than electrical double-layer capacitors while being faster than bulk storage mechanisms.Usually,they suffer from low intrinsic electronic and ion conductivities of the active materials.Here,taking advantage of the combination of TiS2 decoration,sulfur doping,and a nanometer-sized structure,as-spun TiO2/C nanofiber composites are developed that enable rapid transport of sodium ions and electrons,and exhibit enhanced pseudo-capacitively dominated capacities.At a scan rate of 0.5 mV s−1,a high pseudo-capacitive contribution(76%of the total storage)is obtained for the S-doped TiS2/TiO2/C electrode(termed as TiS2/S-TiO2/C).Such enhanced pseudocapacitive activity allows rapid chemical kinetics and significantly improves the high-rate sodium storage performance of TiO2.The TiS2/S-TiO2/C composite electrode delivers a high capacity of 114 mAh g−1 at a current density of 5000 mA g−1.The capacity maintains at high level(161 mAh g−1)even after 1500 cycles and is still characterized by 58 mAh g−1 at the extreme condition of 10,000 mA g−1 after 10,000 cycles.

Morphology-dependent structures and catalytic performances of Au nanostructures on Cu_2O nanocrystals synthesized by galvanic replacement reaction

Au nanostructures were prepared on uniform Cu2O octahedra and rhombic dodecahedra via the galvanic replacement reaction between HAuCl 4 and Cu2O. The compositions and structures were studied by Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), High-Resolution Transmission Electron Microscope (HRTEM), X-Ray Diffraction (XRD), X-Ray Absorption Spectroscopy (XAS), X-ray Photoelectron Spectroscopy (XPS) and in-situ DRIFTS spectroscopy of CO adsorption. Different from the formation of Au-Cu alloys on Cu2O cubes by the galvanic replacement reaction (ChemNanoMat 2 (2016) 861-865), metallic Au particles and positively-charged Au clusters form on Cu2O octahedra and rhombic dodecahedra at very small Au loadings and only metallic Au particles form at large Au loadings. Metallic Au particles on Cu2O octahedra and rhombic dodecahedra are more active in catalyzing the liquid phase aerobic oxidation reaction of benzyl alcohol than positively-charged Au clusters. These results demonstrate an obvious morphology effect of Cu2O nanocrystals on the liquid-solid interfacial reactions and prove oxide morphology as an effective strategy to tune the surface reactivity and catalytic performance. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Revisiting the Role of Physical Confinement and Chemical Regulation of 3D Hosts for Dendrite-Free Li Metal Anode

Lithium metal anode has been demonstrated as the most promising anode for lithium batteries because of its high theoretical capacity,but infinite volume change and dendritic growth during Li electrodeposition have prevented its practical applications.Both physical morphology confinement and chemical adsorption/diffusion regulation are two crucial approaches to designing lithiophilic materials to alleviate dendrite of Li metal anode.However,their roles in suppressing dendrite growth for long-life Li anode are not fully understood yet.Herein,three different Ni-based nanosheet arrays(NiO-NS,Ni_(3)N-NS,and Ni_(5)P_(4)-NS)on carbon cloth as proof-of-concept lithiophilic frame-works are proposed for Li metal anodes.The two-dimensional nanoarray is more promising to facilitate uniform Li^(+)flow and electric field.Compared with the NiO-NS and the Ni_(5)P_(4)-NS,the Ni_(3)N-NS on carbon cloth after reacting with molten Li(Li-Ni/Li_(3)N-NS@CC)can afford the strongest adsorption to Li+and the most rapid Li+diffusion path.Therefore,the Li-Ni/Li_(3)N-NS@CC electrode realizes the lowest overpotential and the most excellent electrochemical performance(60 mA cm^(−2)and 60 mAh cm^(−2)for 1000 h).Furthermore,a remarkable full battery(LiFePO_(4)||Li-Ni/Li_(3)N-NS@CC)reaches 300 cycles at 2C.This research provides valuable insight into designing dendrite-free alkali metal batteries.

Bifunctional TiO2 Catalysts for Efficient Cr（VI） Photoreduction Under Solar Light Irradiation Without Addition of Acids

Bifunctional TiO2 photocatalysts co-doped with nitrogen and sulfur were prepared by the controlled thermal decomposition of ammonium titanyl sulfate precursor. They have both photocatalytic activity and Brφnsted acidity, and thus are active in the photoreduction of Cr（VI） under solar light irradiation without the addition of acids. The activity is superior to that of Degussa P25 in the acidified suspension at the same pH adjusted by H2SO4.

Carbon‐based materials for all‐solid‐state zinc–air batteries

Solid‐state Zn–air batteries(ZABs)hold great potential for application in wearable and flexible electronics.However,further commercialization of current ZABs is still limited by the poor stability and low energy efficiency.It is,thus,crucial to develop efficient catalysts as well as optimize the solid electrolyte system to unveil potential of the ZAB technology.Due to the low cost and versatility in tailoring the structures and properties,carbon materials have been extensively used as the conductive substrates,catalytic air electrodes,and important components in the electrolytes for the solid‐state ZABs.Within this context,we discuss the challenges facing current solid‐state ZABs and summarize the strategies developed to modify properties of carbon‐based electrodes and electrolytes.We highlight the metal−organic framework/covalent organic framework‐based electrodes,heteroatom‐doped carbon,and the composites formed of carbon with metal oxides/sulfides/phosphides.We also briefly discuss the progress of graphene oxide‐based solid electrolyte.

Green synthesis of multifunctional carbon dots for anti-cancer and anti-fungal applications

Carbon dots(CDs)have become popular nanomaterials in biomedical and agricultural fields.Herein we synthesized multifunctional CDs which showed anti-cancer and anti-fungal activities.The low cytotoxicity,stable fluorescence and high photothermal conversion efficiency enable the CDs with imagingguided photothermal therapy.The CDs also exhibited intrinsic anti-fungal activity even at a low concentration,i.e.,40 mg·L^(-1) of CDs induced 20%mortality in cucumber downy mildew.Moreover,the largeπ-conjugated nanostructure and the richness of amino and hydroxyl groups make them a powerful delivery platform for flumorph(a fungicide)with a high loading efficiency of 47.18%.Meanwhile,the heat converted from the light can accelerate the release of flumorph from CDs,and thus efficiently kill fungus.

UV Laser Regulation of Surface Oxygen Vacancy of CoFe2O4 for Enhanced Oxygen Evolution Reaction

Oxygen evolution reaction is one of the key processes in the promising renewable energy technique of electrocatalytic water splitting.Developing high ecient oxygen evolution reaction(OER)catalysts requires determination of the optimal values of the descriptor parameters.Using spinel CoFe2O4 as the model catalyst,this work demonstrates that irradiation with pulsed UV laser can control the quantity of surface oxygen vacancy and thus modify the OER activity,in a volcano-shape evolution trend.This strategy sheds light on quantita-tively investigation of the relationship between surface cation valence,anion vacancy,and physicochemical properties of transition-metal-based compounds.