Metal-organic frameworks with mixed-ligands strategy as heterogeneous nucleation center to assist crystallization for efficient and stable perovskite solar cells

Deep-level defects and random oriented configuration in perovskite crystallization process would cause the nonradiative recombination and further affect the performance of perovskite solar cells(PSCs).Herein,two metal-organic frameworks(MOFs)with tunable Lewis-base passivation sites have been constructed(Cd-Httb and Cd-Httb-BDC,Httb=5-(4-(1H-1,2,4-triazole-1-yl)benzyl)-1h-tetrazole,BDC=1,4-dicarboxybenzene)to eliminate deep-level defects and simultaneously as nanostructured heterogeneous nucleation seed to assist the growth of large-grained perovskite films.Compared with the control and Cd-Httb,Cd-Httb-BDC designed with mix-ligands strategy exhibited the enhanced inducted effect on the crystallization and nucleation of high-quality perovskite films during annealing process.Consequently,the resultant Cd-Httb-BDC-modified device achieved higher power conversion efficiency(PCE)(22.18%)than the control(20.89%)and Cd-Httb(21.56%).Meanwhile,the unencapsulated Cd-Httb-BDC-modified device still maintained 90%of initial PCE after 1500 h in ambient conditions and exhibited enhanced thermal stability(85℃ in N_(2) atmosphere).This work presented a successful example of mixligands strategy on construction of high-quality MOF-assisted perovskite films for high-efficient and stable PSCs.

Multicomponent mixed metallic hierarchical ZnNi@Ni@PEDOT arrayed structures as advanced electrode for high-performance hybrid electrochemical cells

Engineering multicomponent nanomaterials as an electrode with rationalized ordered structures is a promising strategy for fulfilling the high-energy storage needs of supercapacitors(SCs).Even now,the fundamental barrier to utilizing hydroxides/hydroxyl carbonates is their poor electrochemical performance,resulting from the significantly poor electrical conductivity and sluggish charge storage kinetics.Hence,a multilayered structural approach is primarily and successfully used to construct electrodes as one of the efficient approaches.This method has made it possible to develop well-ordered nanostructured electrodes with good performance by taking advantage of tunable approach parameters.Herein,we report the design of multilayered heterostructure porous zinc-nickel nanosheets@nickel flakes hydroxyl carbonates and/or hydroxides integrated with conductive PEDOT fibrous network(i.e.,ZnNi@Ni@PEDOT) via facile synthesis methods.The combined hybrid electrode acquires the features of high electrical conductivity from one part and various valance states from another one to develop a well-organized nanosheet/flake/fibrous-like heterostructure with decent mechanical strength,creating robust synergistic results.Thus,the designed binder-free ZnNi@Ni@PEDOT electrode delivers a high areal capacity value of 1050.1 μA h cm^(-2) at 3 mA cm^(-2) with good cycling durability,significantly outperforming other individual electrodes.Moreover,its feasibility is also tested by constructing a hybrid electrochemical cell(HEC).The assembled HEC exhibits a high areal capacity value of 783.8 μA h cm^(-2) at5 mA cm^(-2).and even at a high current density of 100 mA cm^(-2)(484.6 μA h cm^(-2)),the device still retains a rate capability of 61,82%,Also,the HEC shows maximum energy and power densities of0.595 mW h cm^(-2) and 77.23 mW cm^(-2),respectively,along with good cycling stability.The obtained energy storage capabilities effectively power various electronic components.These results provide a viable and practical way to construct a positive electrode with innovative heterostructures for highperformance energy storage devices and profoundly influence the development of electrochemical SCs.

12.6μm-Thick Asymmetric Composite Electrolyte with Superior Interfacial Stability for Solid-State Lithium-Metal Batteries

Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes,and to minimize the electrolyte thickness to achieve highenergy-density of SSLMBs.Herein,we develop an ultrathin(12.6μm)asymmetric composite solid-state electrolyte with ultralight areal density(1.69 mg cm^(−2))for SSLMBs.The electrolyte combining a garnet(LLZO)layer and a metal organic framework(MOF)layer,which are fabricated on both sides of the polyethylene(PE)separator separately by tape casting.The PE separator endows the electrolyte with flexibility and excellent mechanical properties.The LLZO layer on the cathode side ensures high chemical stability at high voltage.The MOF layer on the anode side achieves a stable electric field and uniform Li flux,thus promoting uniform Li^(+)deposition.Thanks to the well-designed structure,the Li symmetric battery exhibits an ultralong cycle life(5000 h),and high-voltage SSLMBs achieve stable cycle performance.The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg^(−1)/773.1 Wh L^(−1).This simple operation allows for large-scale preparation,and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.

Fe-N-C core-shell catalysts with single low-spin Fe(Ⅱ)-N_(4)species for oxygen reduction reaction and high-performance proton exchange membrane fuel cells

Fe-N-doped carbon materials(Fe-N-C)are promising candidates for oxygen reduction reaction(ORR)relative to Pt-based catalysts in proton exchange membrane fuel cells(PEMFCs).However,the intrinsic contributions of Fe-N_(4)moiety with different chemical/spin states(e.g.D1,D2,D3)to ORR are unclear since various states coexist inevitably.In the present work,Fe-N-C core-shell nanocatalyst with single lowspin Fe(Ⅱ)-N_(4)species(D1)is synthesized and identified with ex-situ ultralow temperature Mossbauer spectroscopy(T=1.6 K)that could essentially differentiate various Fe-N_(4)states and invisible Fe-O species.By quantifying with CO-pulse chemisorption,site density and turnover frequency of Fe-N-C catalysts reach 2.4×10^(-9)site g^(-1)and 23 e site~(-1)s^(-1)during the ORR,respectively.Half-wave potential(0.915V_(RHE))of the Fe-N-C catalyst is more positive(approximately 54 mV)than that of Pt/C.Moreover,we observe that the performance of PEMFCs on Fe-N-C almost achieves the 2025 target of the US Department of Energy by demonstrating a current density of 1.037 A cm^(-2)combined with the peak power density of 0,685 W cm^(-2),suggesting the critical role of Fe(Ⅱ)-N_(4)site(D1).After 500 h of running,PEMFCs still deliver a power density of 1.26 W cm^(-2)at 1.0 bar H_(2)-O_(2),An unexpected rate-determining step is figured out by isotopic labelling experiment and theoretical calculation.This work not only offers valuable insights regarding the intrinsic contribution of Fe-N_(4)with a single spin state to alkaline/acidic ORR,but also provides great opportunities for developing high-performance stable PEMFCs.

Heterojunction Incorporating Perovskite and Microporous Metal–Organic Framework Nanocrystals for Efficient and Stable Solar Cells

In this paper,we present a facile approach to enhance the efficiency and stability of perovskite solar cells(PSCs)by incorporating perovskite with microporous indium-based metal–organic framework[In12O(OH)16(H2O)5(btc)6]n(In-BTC)nanocrystals and forming heterojunction light-harvesting layer.The interconnected micropores and terminal oxygen sites of In-BTC allow the preferential crystallization of perovskite inside the regular cavities,endowing the derived films with improved morphology/crystallinity and reduced grain boundaries/defects.Consequently,the In-BTC-modified PSC yields enhanced fill factor of 0.79 and power conversion efficiency(PCE)of 20.87%,surpassing the pristine device(0.76 and 19.52%,respectively).More importantly,over 80%of the original PCE is retained after 12 days of exposure to ambient environment(25°C and relative humidity of^65%)without encapsulation,while only about 35%is left to the pristine device.

Effects of environmental factors on corrosion behaviors of metal-fiber porous components in a simulated direct methanol fuel cell environment

Abstract： To enable the use of metallic components in direct methanol fuel cells （DMFCs）, issues related to corrosion resistance must be considered because of an acid environment induced by the solid electrolyte. In this study, we report the electrochemical behaviors of metal-fiber-based porous sintered components in a simulated corrosive environment of DMFCs. Three materials were evaluated： pure copper, AISI304, and AISI316L. The environmental factors and related mechanisms affecting the corrosion behaviors were analyzed. The results demonstrated that AISI316L exhibits the best performance. A higher SO4^2- concentration increases the risk of material corrosion, whereas an increase in methanol concentration inhibits corrosion. The morphological features of the corroded samples were also characterized in this study.

Plating current density distribution of lithium metal anodes in pouch cells

The uniformity of current density distribution upon electrodes is one of the most important factors determining the lithium dendrites growth and cycling performance of lithium metal batteries(LMBs). Herein,current density distributions of lithium metal anodes induced by various engineering factors, consisting of uneven cathode, electrolyte distribution, and different tab positions, and their effects on the electrochemical performance are investigated theoretically and experimentally in pouch cells. The deviation of current density in lithium metal anodes ranges from 2.47% to 196.18% due to the different levels of uneven cathode materials. However, the deviation is just 13.60% for different electrolyte thicknesses between cathodes and anodes, even a ten-layer separator in some positions. The maximum deviation for variational tab positions is only 0.17%. The nonuniformity in current density distribution results in severe dendrite growth issues and poor electrochemical performance of LMBs. This work not only confirms the direct correlation between the uneven current density distribution and lithium deposition behaviors, but also points out the decisive effects of cathode surface roughness on current distribution of anodes, to which more attentions should be paid in practical applications of LMBs.

High efficiency and stable solid-state fiber dye-sensitized solar cells obtained using TiO_(2) photoanodes enhanced with metal organic frameworks

Solid-state fiber dye-sensitized solar cells(SS-FDSSCs) have been the subject of intensive attention and development in recent years. Although this field is only in its infancy, metal–organic frameworks(MOFs) are one such material that has been utilized to further improve the power conversion efficiency of solar cells. In this study, MOF-integrated DSSCs were shown to have potential in the development of solar cell devices with efficiency comparable to or better than that of conventional solar cells. The power conversion efficiency(PCE) of SS-FDSSCs was improved by embedding MOF-801 into a mesoporous-TiO_(2)(mp-TiO_(2)) layer, which was used as a photoanode in SS-FDSSCs, which are inherently flexible. The PCE of the MOF-integrated SS-FDSSCs was 6.50%, which is comparable to that of the reference devices(4.19%).The MOF-801 enhanced SS-FDSSCs decreased the series resistance(R_(s)) value, resulting in effective electron extraction with improved short-circuit current density(J_(SC)), while also increasing the shunt resistance(R_(sh)) value to prevent the recombination of photo-induced electrons. The result is an improved fill factor and, consequently, a higher value for the PCE.

Review on transition metal compounds based counter electrode for dye-sensitized solar cells

Commercial application of the dye-sensitized solar cells（DSCs） depends on great improvement of the power conversion efficiency and reduction of the fabrication cost. Generally, developing low cost counter electrode catalysts to replace the expensive Pt counter electrode is a feasible path to reduce the production cost of DSCs. In this review article, we summarize the recent progress on the transition metal compound based counter electrode catalysts containing carbides, nitrides, oxides, sulfides, phosphide, selenides, borides, silicide, and telluride toward the regeneration of the traditional iodide redox couple.Moreover, the benefits and drawbacks of each kind of CE catalyst are discussed and the research directions to design new counter electrode catalysts in future research are also proposed.

Toxicity assessment of heavy metals and organic compounds using CellSense biosensor with E.coli

A new strategy using an arnperometric biosensor with Escherichia coli （E. coli） that provides a rapid toxicity determination of chemical compounds is described. The CellSense biosensor system comprises a biological component immobilized in intimate contact with a transducer which converts the biochemical signal into a quantifiable electrical signal. Toxicity assessment of heavy metals using E.coli biosensors could be finished within 30 min and the 50% effective concentrations （ECso） values of four heavy metals were determined. The results shows that inhibitory effects of four heavy metals to E.coli can be ranked in a decreasing order of Hg^2＋ 〉 Cu^2＋ 〉 Zn^2＋ 〉 Ni^2＋, which accords to the results of conventional bacterial counting method. The toxicity test of organic compounds by using CellSense biosensor was also demonstrated. The CellSense biosensor with E. coli shows a good, reproducible behavior and can be used for reproducible measurements.

Metallothionein Genes in the Nematode Caenorhabditis elegans and Metal Inducibility in Mammalian Culture Cells

Genomic DNAs of metallothionein Ⅰ and Ⅱ in Caenorhabditis elegans (CeMT-Ⅰand CeMT-Ⅱ) were isolated by YAC library/polytene filter hybridization followed by subcloning of corresponding cosmid clones. Both genes are mapped at chromosome V. Although the similarities of 5'-flanking regions and coding regions have shown only 55-58%, the introns are split at the same position in both genes, indicating that these two genes are originally from the same gene. While several metal responsive elements are conserved among eukaryotes, only one metal responsive element was found in the promoter region in CeMT-Ⅱ and not in CeMT-Ⅰ. Indced, neither of 5'-flanking regions of CeMT-Ⅰ nor CeMT-Ⅱ connected to chloramphenicol acetyltransferase reporter gene is responsive to heavy metals in mammalian culture cells by transient transfection analysis. These results would suggest that the metal regulatory factors in C.elegans might be different from those conserved in invertebrates and vertebrates, although the MTs in C elegans revealed the similarities to mammalian MTs in several points

Highly soluble organic nitrate additives for practical lithium metal batteries

The stability of lithium metal anodes essentially dictates the lifespan of high-energy-density lithium metal batteries.Lithium nitrate(LiNO_(3))is widely recognized as an effective additive to stabilize lithium metal anodes by forming LiN_(x)O_(y)-containing solid electrolyte interphase(SEI).However,its poor solubility in electrolytes,especially ester electrolytes,hinders its applications in lithium metal batteries.Herein,an organic nitrate,isosorbide nitrate(ISDN),is proposed to replace LiNO_(3).ISDNhas a high solubility of 3.3M in ester electrolytes due to the introduction of organic segments in the molecule.The decomposition of ISDN generates LiN_(x)O_(y)-rich SEI,enabling uniform lithium deposition.The lifespan of lithium metal batteries with ISDN significantly increases from 80 to 155 cycles under demanding conditions.Furthermore,a lithium metal pouch cell of 439Whkg^(−1) delivers 50 cycles.This work opens a new avenue to develop additives by molecular modifications for practical lithium metal batteries.

Improving the stability of metal halide perovskite solar cells from material to structure

Metal halide perovskites(MHPs) are promising photovoltaic(PV) materials owing to their advantages such as high carrier mobility, excellent absorption coefficient, bandgap tenability, long diffusion length,and low material cost. These qualities have increased the efficiency of MHP solar cells to 23.3%. However,MHPs are hindered by a lack of stability. In addition, the applications of MHP solar cells are restricted by the instability of perovskite materials and devices. In this article, the most urgent stability problems faced by perovskite solar cells are identified, and recent progresses in MHPs are enumerated. The factors affecting the stability of perovskite materials and devices are also discussed. We analyzed the thermal and humid stability of perovskite materials in terms of transporting materials and their interface. In view of these recent advances, future works should focus on the large-scale application of MHP solar cells.

Thermal modeling and the optimized design of metal plate cooling systems for single concentrator solar cells

A metal plate cooling model for 400~ single concentrator solar cells was established. The effects of the thickness and the radius of the metal plate, and the air environment on the temperature of the solar cells were analyzed in detail. It is shown that the temperature of the solar cells decreased sharply at the beginning, with the increase in the thickness of the metal plate, and then changed more smoothly. When the radius of the metal plate was 4 cm and the thickness increased to 2 mm or thicker, the temperature of the solar cell basically stabilized at about 53℃. Increasing the radius of the metal plate and the convective transfer coefficient made the temperature of the solar cell decrease remarkably. The effects of A1 and Cu as the metal plate material on cooling were analyzed contrastively, and demonstrated the superiority of A1 material for the cooling system. Furthermore, considering cost reduction, space holding and the stress of the system, we optimized the structural design of the metal plate. The simulated results can be referred to the design of the structure for the metal plate. Finally, a method to devise the structure of the metal plate for single concentrator solar cells was given.

Effects of some heavy metals on cell suspension cultures of Catharanthus roseus

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Review： Perspectives on the metallic interconnects for solid oxide fuel cells

The various stages and progress in the development of interconnect materials for solid oxide fuel cells (SOFCs )over the last two decades are reviewed. The criteria for the application of materials as interconnects are highlighted. Interconnects based on lanthanum chromite ceramics demonstrate many inherent drawbacks and therefore are only useful for SOFCs operating around 1000℃. The advance in the research of anode-supported flat SOFCs facilitates the replacement of ceramic interconnects with metallic ones due to their significantly lowered working temperature. Besides, interconnects made of metals or alloys offer many advantages as compared to their ceramic counterpart. The oxidation response and thermal expansion behaviors of various prospective metallic interconnects are examined and evaluated. The minimization of contact resistance to achieve desired and reliable stack performance during their projected lifetime still remains a highly challenging issue with metallic interconnects. Inexpensive coating materials and techniques may play a key role in promoting the commercialization of SOFC stack whose interconnects are constructed of some current commercially available alloys. Alternatively, development of new metallic materials that are capable of forming stable oxide scales with sluggish growth rate and sufficient electrical conductivity is called for.

Fabrication of Gd_(2)O_(3)-doped CeO_(2)thin films through DC reactive sputtering and their application in solid oxide fuel cells

Physical vapor deposition(PVD)can be used to produce high-quality Gd_(2)O_(3)-doped CeO2(GDC)films.Among various PVD methods,reactive sputtering provides unique benefits,such as high deposition rates and easy upscaling for industrial applications.GDC thin films were successfully fabricated through reactive sputtering using a Gd_(0.2)Ce_(0.8)(at%)metallic target,and their application in solid oxide fuel cells,such as buffer layers between yttria-stabilized zirconia(YSZ)/La0.6Sr0.4Co0.2Fe0.8O_(3−δ)and as sublayers in the steel/coating system,was evaluated.First,the direct current(DC)reactive-sputtering behavior of the GdCe metallic target was determined.Then,the GDC films were deposited on NiO-YSZ/YSZ half-cells to investigate the influence of oxygen flow rate on the quality of annealed GDC films.The results demonstrated that reactive sputtering can be used to prepare thin and dense GDC buffer layers without high-temperature sintering.Furthermore,the cells with a sputtered GDC buffer layer showed better electrochemical performance than those with a screen-printed GDC buffer layer.In addition,the insertion of a GDC sublayer between the SUS441 interconnects and the Mn-Co spinel coatings contributed to the reduction of the oxidation rate for SUS441 at operating temperatures,according to the area-specific resistance tests.

Recent advances in regulating the performance of acid oxygen reduction reaction on carbon-supported non-precious metal single atom catalysts

Developing high performance and low-cost catalysts for oxygen reduction reaction(ORR)in challenging acid condition is vital for proton-exchange-membrane fuel cells(PEMFCs).Carbon-supported nonprecious metal single atom catalysts(SACs)have been identified as potential catalysts in the field.Great advance has been obtained in constructing diverse active sites of SACs for improving the performance and understanding the fundamental principles of regulating acid ORR performance.However,the ORR performance of SACs is still unsatisfactory.Importantly,microenvironment adjustment of SACs offers chance to promote the performance of acid ORR.In this review,acid ORR mechanism,attenuation mechanism and performance improvement strategies of SACs are presented.The strategies for promoting ORR activity of SACs include the adjustment of center metal and its microenvironment.The relationship of ORR performance and structure is discussed with the help of advanced experimental investigations and theoretical calculations,which will offer helpful direction for designing advanced SACs for ORR.

The effect of transition metal ions (M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis polyaniline as counter electrodes in dye-sensitized solar cells

The effect of transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis of polyaniline(PANI) used as a platinum-free counter electrode(CE) in dye-sensitized solar cells(DSSCs) was investigated.PANI was synthesized by co-polymerization of aniline in the presence of different transition metal ions by using potassium dichromate in acidic medium. It was found that the ion doping of PANI showed a certain catalytic activity for the regeneration of traditional iodide/triiodide(I^-/I_3^-) redox couples. The power conversion efficiency(η) of PANI CEs doped with Mn^(2+),Ni^(2+),Co^(2+) (4.41%, 2.36% and 2.10%, respectively) were higher than 1.94%, the value measured for PANI CE without doping. Doping with Cu^(2+)decreased the power conversion efficiency of PANI CE(PANI-Cu^(2+) η = 1.41%). The electrical properties of the PANI, PANI-Ni^(2+), PANI-Co^(2+),PANI-Mn^(2+) and PANI-Cu^(2+) were studied by cyclic voltammetry(CV), impedance(EIS), and Tafel polarization curve. The experimental results confirmed that PANI was affected by the doping of different transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)). These results indicate a potential application of ion doped PANI as counter electrode in cost-effective DSSCs.

Numerical simulation of current distribution in metal pad of aluminum reduction cells

Based on the numerical calculation of 3-D potential distribution in aluminum reduction cells, current distribution in the metal pad is calculated under the following conditions: 1) pot ledge ideally formed; 2) ledge extension to below anode; 3) different metal heights; 4) AC and 5) Spike. It is found that J_y in metal pad increases first to a highest point and then decreases along anode length. At normal status, the largest J_y is about 0.4A/cm^2 and it locates at about 2/3 of anode length. With longer ledge, the maximum value of J_y decreases and its position moves center-ward. The longer the side ledge, the larger the negative current flowing center-ward at side channel. J_z in metal pad increases with anode length and it is not affected by metal height; while J_y increases with metal height. At AC, current flows toward metal under new anode. At spike, current concentrates at spike rather than evenly distributes. Normally, J_x is almost negligible in metal pad.