A homogeneous and mechanically stable artificial diffusion layer using rigid-flexible hybrid polymer for high-performance lithium metal batteries

Artificial solid electrolyte interphase(SEI) is promising to inhibit uncontrollable lithium dendrites and enable long cycling stability for lithium metal batteries. However, the essential mechanical stability is limited since organic layers generally have low modulus whereas intrinsic brittleness for inorganic ones remains a great concern. Polymer-based SEIs with rigid and flexible chains in adequate mechanical properties are supposed to address this issue. Herein, a homogeneous and mechanically stable diffusion layer is achieved by blending rigid chains of polyphenylene sulfone(PPSU) with flexible chains of poly(vinylidene fluoride)(PVDF) in a hybrid membrane, enabling uniform diffusion and stabilizing the lithium metal anode. The Li||Cu cell with the protected electrode exhibits a long lifetime more than 450 cycles(0.5 m A cm^(-2), 1.0 m A h cm^(-2))(fourfold longer than the control group) with higher average Coulombic efficiency of 98.7%. Enhanced performances are also observed at Li||Li and full cell configurations. The improved performances are attributed to the controlled morphology and stable interphase, according to scanning electron microscopy(SEM) and electrochemical impedance. This research advances the idea of uniform lithium plating and provides a new insight on how to create a homogeneous and mechanically stable diffusion layer using rigid-flexible polymers.

Nanoscale transition metal catalysts anchored on perovskite oxide enabling enhanced kinetics of lithium polysulfide redox in lithium-sulfur batteries

To obtain high-performance lithium-sulfur(Li-S)batteries,it is necessary to rationally design electrocatalytic materials that can promote efficient sulfur electrochemical reactions.Herein,the robust heterostructured material of nanoscale transition metal anchored on perovskite oxide was designed for efficient catalytic kinetics of the oxidation and reduction reactions of lithium polysulphide(Li PSs),and verified by density functional theory(DFT)calculations and experimental characterizations.Due to the strong interaction of nanoscale transition metals with Li PSs through chemical coupling,heterostructured materials(STO@M)(M=Fe,Ni,Cu)exhibit excellent catalytic activity for redox reactions of Li PSs.The bifunctional heterostructure material STO@Fe exhibits good rate performance and cycling stability as the cathode host,realizing a high-performance Li-S battery that can maintain stable cycling under rapid charge-discharge cycling.This study presents a novel approach to designing electrocatalytic materials for redox reactions of Li PSs,which promotes the development of fast charge-discharge Li-S batteries.

Progress and challenges of carbon-fueled solid oxide fuel cells anode

Carbon-fueled solid oxide fuel cells(CF-SOFCs)can electrochemically convert the chemical energy in carbon into electricity,which demonstrate both superior electrical efficiency and fuel utilisation compared to all other types of fuel cells.However,using solid carbon as the fuel of SOFCs also faces some challenges,the fluid mobility and reactive activity of carbon-based fuels are much lower than those of gaseous fuels.Therefore,the anode reaction kinetics plays a crucial role in determining the electrochemical performance of CF-SOFCs.Herein,the progress of various anodes in CF-SOFCs is reviewed from the perspective of material compositions,electrochemical performance and microstructures.Challenges faced in developing high performance anodes for CF-SOFCs are also discussed.

Catalytic performance of hierarchical H-ZSM-5/MCM-41 for methanol dehydration to dimethyl ether

Micro-mesoporous composite molecular sieves H-ZSM-5/MCM-41 were prepared by the hydrothermal technique with alkali-treated H-ZSM-5zeolite as the source and characterized by scanning electron microscopy,transmission electron microscopy,energy dispersive spectroscopy,X-ray diffraction,N2 adsorption-desorption measurement and NH3 temperature-programmed desorption.The catalytic performances for the methanol dehydration to dimethyl ether over H-ZSM-5/MCM-41 were evaluated.Among these catalysts,H-ZSM-5/MCM-41 prepared with NaOH dosage (nNa/nSi) varying from 0.4 to 0.47 presented excellent catalytic activity with more than 80%methanol conversion and 100%dimethyl ether selectivity in a wide temperature range of 170—300℃,and H-ZSM-5/MCM-41 prepared with nNa/nSi=0.47 showed constant methanol conversion of about 88.7%,100% dimethyl ether selectivity and excellent lifetime at 220℃.The excellent catalytic performances were due to the highly active and uniform acidic sites and the hierarchical porosity in the micro-mesoporous composite molecular sieves.The catalytic mechanism of H-ZSM-5/MCM-41 for the methanol dehydration to dimethyl ether process was also discussed.

PIM-1 as an artificial solid electrolyte interphase for stable lithium metal anode in high-performance batteries

Lithium metal anode is a promising electrode with high theoretical specific capacity and low electrode potential.However,its unstable interface and low Coulombic efficiency,resulting from the dendritic growth of lithium,limits its commercial application.PIM-1(PIM:polymer of intrinsic microporosity),which is a polymer with abundant micropores,exhibits high rigidity and flexibility with contorted spirocenters in the backbone,and is an ideal candidate for artificial solid electrolyte interphases(SEI).In this work,a PIM-1 membrane was synthesized and fabricated as a protective membrane on the surface of an electrode to facilitate the uniform flux of Li ions and act as a stable interface for the lithium plating/stripping process.Nodule-like lithium with rounded edges was observed under the PIM-1 membrane.The Li@PIM-1 electrode delivered a high average Coulombic efficiency(99.7%),excellent cyclability(80%capacity retention rate after 600 cycles at 1 C),and superior rate capability(125.3 m Ah g-1 at 10 C).Electrochemical impedance spectrum(EIS)showed that the PIM-1 membrane could lower the diffusion rate of Li+significantly and change the rate-determining step from charge transfer to Li+diffusion.Thus,the PIM-1 membrane is proven to act as an artificial SEI to facilitate uniform and stable deposition of lithium,in favor of obtaining a compact and dense Li-plating pattern.This work extends the application of PIMs in the field of lithium batteries and provides ideas for the construction of artificial SEI.

Upgrading Siberian(Russia)crude oil by hydrodesulfurization in a slurry reactor:A kinetic study

Hydrodesulfurization(HDS)of sour crude oil is an effective way to address the corrosion problems in refineries,and is an economic way to process sour crude oil in an existing refinery built for sweet oil.In the current study,the HDS of Siberian crude oil was carried out in a slurry reactor.The Co-Mo,Ni-Mo,and Ni-W catalysts supported onγ-Al2O3 were compared at the temperature of 340℃ and the pressure of 4.5 MPa.The HDS activity follows the order of Co-Mo N Ni-Mo N Ni-Wat a high concentration of H2S,and the difference between Co-Mo and Ni-Mo becomes insignificant at a low concentration of H2S.The influence of reaction temperature 320-360℃ and reaction pressure 3-5.5 MPa was investigated,and both play a positive role in the HDS reaction.A kinetic model over Ni-Mo/Al2O3 in the slurry reactor was established.The activation energy is estimated as 60.34 kJ·mol−1;the orders of sulfur components and hydrogen partial pressure are 1.43 and 1.30,respectively.The kinetic parameters are compared with those in a trickle-bed reactor,implying that the mass transfer is greatly enhanced in the slurry reactor.The back mixing effect is present in the slurry reactor and can be reduced by a multi-stage design,which would lead to higher reactor efficiency in industrial application.

Investigation of polysulfone film on high-performance anode with stabilized electrolyte/electrode interface for lithium batteries

Lithium metal has been considered to be the most promising anode material for the new generation of energy-storage system.However,challenges still stand in protecting lithium metal from spontaneous reactions with electrolytes and preventing the dendritic propagation,both of which would lead to undesirable decrease in Coulombic efficiency.Polysulfone(PSf)membrane with high rigidity and free-volume cavities of approximately 0.3 nm was employed to provide a stable interface on the surface of anodic electrode.The isotropic channels were constructed by the interconnected and uniformly distributed free volumes in the polymer matrix,and were expected to be swelled by solvent molecules and anions of lithium salt and to allow Li+ions to pass through onto the electrode surface.As a result,dendrite-free morphology of deposited lithium was observed.The stabilized interface arose from the PSf film was verified by the promoted performances of Cu|Li cells and steady voltage polarization of Li|Li cells.The full cell with PSf coated anode exhibited excellent cyclability(85%capacity retention rate over 400 cycles at 1C)and an outstanding rate capability(117 m Ah g-1 at 5C).The beneficial performances were further verified by the EIS results.This work provides a new strategic idea to settle the dendritic problems of Li metal anodes.

Porous conductive interlayer for dendrite-free lithium metal battery

Lithium(Li) metal,possessing ultrahigh theoretical capacity and the lowest electrode potential,is regarded as a promising new generation anode material.However,the uncontrollable growth of Li dendrites during cycling process gives rise to problems as capacity decay and short circuit,suppressing the cycling and safety performances of Li metal battery.In this contribution,porous conductive interlayer(PCI),composed of carbon nanofibers(CNFs) and polyisophthaloyl metaphenylene diamine(PMIA),is developed to suppress Li dendrites and stabilize Li metal anode.PCI possesses the excellent conductive ability of CNFs and the preeminent mechanical properties of PMIA at the same time.When Li metal contacts with PCI during cycling process,an equipotential surface forms on their interface,which eliminates the tip effect on Li anode and homogenizes Li-ions flux in combination with the uniform porous structure of PCI.Employed PCI,the Li|Cu cell exhibits a remarkable cycling stability with a high average Coulombic efficiency of 97.5% for 100 cycles at 0.5 mA cm^(-2).And the Li|LiFePO_4 cell exhibits improved rate capability(114.7 mAh g^(-1) at 5.0 C) and enhanced cycling performance(78.9% capacity retention rate over 500 cycles at 1.0 C).This work provides a fresh and effective solving strategy for the problem of dendrites in Li metal battery.

自清洁钙钛矿型催化剂用于甲烷干气重整(英文)

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass‐derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e.,CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid cok‐ing. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

Enhancing anchoring and catalytic conversion of polysulfides by nitrogen deficient cobalt nitride for advanced lithium-sulfur batteries

While lithium-sulfur(Li-S)battery has attracted remarkable attention owing to the high theoretical capacity,its practical application is still hindered by the shuttle and sluggish conversion kinetics of intermediate lithium polysulfides(Li PSs).Defect engineering,which can regulate the electronic structure and in turn influence the surface adsorption and catalytic capability,has been regarded as a feasible strategy to deal with the above challenges.However,few studies on nitrogen vacancies and their mechanisms are reported.Herein,cobalt nitride with nitrogen vacancies grown on multi-walled carbon nanotube(CNTCo N-VN)is designed and applied as the separator modification material to investigate the enhancing mechanism of nitrogen vacancies on Li-S batteries.The experimental evidence and theoretical calculation indicate that the introduction of nitrogen vacancies into cobalt nitride can enhance the chemical affinity to Li PSs and effectively hamper the shuttle effect.Meanwhile the reduced band gap of the d-band center of Co and p-band center of N for CNT-Co N-VNand the promoted diffusion of Li^(+) can expedite the solid-liquid and liquid-liquid conversions of sulfur species.Due to these superiorities,the cell with CNT-Co NVNmodified separator delivers a favorable initial capacity of 901 m Ah g^(-1)and a capacity of 660 m Ah g^(-1)can be achieved after 250 cycles at 2 C.This work explores the application of metal nitride with nitrogen vacancies and sheds light on the development of functional separators for high-efficient Li-S batteries.

A robust interface enabled by electrospun membrane with optimal resistance in lithium metal batteries

A uniform diffusion layer is essential for non-dendritic deposition of lithium in high-density lithium batteries.However,natural pristine solid electrolyte interface(SEI)is always porous and inhomogeneous because of repeated breakdown and repair cycles,whereas ideal materials with excellent mechanical property for artificial SEIs remain a challenge.Herein,a robust and stable interface is achieved by spinning soft polymer associated with few MoO_(3) into fibers,and thus mechanical property of fibers other than materials determines mechanical performance of the interface which can be optimized by adjusting parameters.Furthermore,lithium deposited underneath the layer is enabled by constructing an optimal resistance to make the membrane serve as an artificial SEI rather than lithium host.As a result,dendritefree lithium was observed underneath the membrane,and stable interface for long-term cycling was also indicated by EIS measurements.The lithium iron phosphate(LiFePO_(4))full-cell with coated electrode demonstrated an initial capacity of 155.2 m Ah g^(-1),and 80%of its original capacity was retained after 500 cycles at 2.0℃ without any additive in carbonate-based electrolyte.

Transition Metal Doped MnO_x-CeO₂Catalysts by Ultrasonic Immersing for Selective Catalytic Reduction of NO with NH₃at Low Temperature

Transition metals doped Mn-based catalysts were prepared via ultrasonic immersing method for the selective catalytic reduction (SCR) of NOx from fuel gas. The Catalysts’ DeNOx efficiency and tolerance to sulfur were investigated in the paper. XRD results demonstrate high dispersion of Mn, Ce and M (Pr, Y, Zr, W) elements on TiO2 carrier, which is favor for reduction of active materials content. Mn-Ce-W catalyst presents uniform particle size about 500 nm to 800 nm from SEM pictures and shows the best NOx conversion of 93.2% at 200°C and 98.4% at 250°C, respectively. Sulfur tolerance analysis indicated that transition metals M can improve the catalysts’ performance when 0.01% SO2 exists in the fuel gas, because metal doping into the Mn-Ce catalyst can inhibit the sulfate deposition, especially metal sulfate, on the catalyst, which can be seen from the Fourier infrared spectrum.

Upgrading Siberian(Russia) crude oil by hydrodesulfurization: Kinetic parameter estimation in a trickle-bed reactor

Hydrodesulfurization(HDS) of sour crude oil is an effective way to address the corrosion problems in refineries and is an economic way to process sour crude oil in an existing refinery built for sweet oil.Siberian crude oil transported through the Russia-China pipeline could be greatly sweetened and could be refined directly in local refinery designed for Daqing crude oil after the effective HDS treatment.In this study,the HDS of Siberian crude oil was carried out in a continuous flow isothermal trickle-bed reactor over Ni-Mo/γ-Al_2 O_(3).The effects of temperature,pressure and LHSV were investigated in the ranges of 320-360℃,3-5 MPa and 0.5-2 h^(-1),keeping constant hydrogen to oil ratio at 600 L·L^(-1).The HDS conversion could be up to 92.89% at the temperature of 360℃, pressure of 5 MPa,and LHSV of 0.5 h^(-1), which is sufficient for local refineries(>84%).A three phase heterogeneous model was established to analyze the performance of the trickle-bed reactor based on the two-film theory using Langmuir-Hinshelwood mechanism.The order of sulfur component is estimated as 1.28,and the order of hydrogen is 0.39.By simulating the reactor using the established model,the concentration of H_(2), H_(2) S and sulfur along the catalyst bed is discussed.The model is significantly useful for industrial application with respect to reactor analysis,optimization and reactor design,and can provide further insight of the HDS of Siberian crude oil.

Barium-doped Pr_(2)Ni_(0.6)Cu_(0.4)O_(4+δ) with triple conducting characteristics as cathode for intermediate temperature proton conducting solid oxide fuel cell

Proton conducting solid oxide fuel cell(H-SOFC)is an emerging energy conversion device,with lower activation energy and higher energy utilization efficiency.However,the deficiency of highly active cathode materials still remains a major challenge for the development of H-SOFC.Therefore,in this work,K_(2)NiF_(4)-type cathode materials Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ)(x=0,0.1,0.2,0.3),single-phase tripleconducting(e-/O^(2-)/H^(+))oxides,are prepared for intermediate temperature H-SOFCs and exhibit good oxygen reduction reaction activity.The investigation demonstrates that doping Ba into Pr_(2-x)BaxNi_(0.6)Cu_(0.4)O_(4+δ) can increase its electrochemical performance through enhancing electrical conductivity,oxygen vacancy concentration and proton conductivity.EIS tests are carried at 750℃ and the minimum polarization impedances are obtained when x=0.2,which are 0.068 Ω·cm^(2) in air and 1.336 Ω·cm^(2) in wet argon,respectively.The peak power density of the cell with Pr_(1.8)Ba_(0.2)Ni_(0.6)Cu_(0.4)O_(4+δ) cathode is 298 mW·cm^(-2) at 750℃ in air with humidified hydrogen as fuel.Based on the above results,Ba-doped Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ) can be a good candidate material for SOFC cathode applications.

Ultrathin two-dimensional bimetal NiCo-based MOF nanosheets as ultralight interlayer in lithium-sulfur batteries

Lithium-sulfur batteries as one of the most promising next-generation high-energy storage system, the shuttle effect, the expansion of cathode and the slow electrode redox kinetics limit its further development. Herein, we report a two-dimensional, ultrathin and ultra-light bimetal-Ni Co-organic framework as the interlayer for Li-S batteries. This kind of interlayer can effectively block polysulfides and accelerate the conversion with a thickness of only 1 μm and a load of 0.1 mg/cm^(2). Because the MOF nanosheets with a thickness of a few nanometers have a large specific surface and a large number of exposed accessible active sites. At the same time, the intrinsic activity of each site is enhanced and the catalytic performance is improved due to the synergistic effect of mixed metals and the unique coordination environment around the active sites. So, 2D NiCo MOF/CNT totally meets the requirements for the lightweight and effective interlayer. The initial discharge capacity of cell with 2D NiCo MOF/CNT interlayer can reach 1132.7 m Ah/g at 0.5 C. It remained 709.1 m Ah/g after 300 cycles, showing good cycling stability and rate performance.

High-entropy perovskite oxide BaCo_(0.2)Fe_(0.2)Zr_(0.2)Sn_(0.2)Pr_(0.2)O_(3-δ) with triple conduction for the air electrode of reversible protonic ceramic cells

Reversible protonic ceramic cells(RPCCs) show great potential as new-generation energy conversion and storage devices. However, the mature development of RPCCs is seriously hindered by the inactivity and poor stability of air electrodes exposed to concentrated vapor under operating conditions. Herein, we report a high-entropy air electrode with the composition BaCo_(0.2)Fe_(0.2)Zr_(0.2)Sn_(0.2)Pr_(0.2)O_(3-δ)(BCFZSP), which shows integrated electronic, protonic and oxygenic conduction in a single perovskite phase and excellent structural stability in concentrated steam. Such triple conduction can spread the electrochemically active sites of the air electrode to the overall electrode surface, thus optimizing the kinetics of the oxygen reduction and evolution reactions(0.448 Ω cm^(2) of polarization resistance at 550℃). As-prepared RPCCs with a BCFZSP air electrode at 600℃ achieved a peak power density of 0.68 W/cm^(2) in fuel-cell mode and a current density of 0.92 A/cm^(2) under a 1.3 V applied voltage in electrolysis mode. More importantly, the RPCCs demonstrate an encouragingly high stability during 120 h of reversible switching between the fuelcell and electrolysis modes. Given their excellent performance, high-entropy perovskites can be promising electrode materials for RPCCs.

Enhancing electrochemical conversion of lithium polysulfide by 1T-rich MoSe_(2) nanosheets for high performance lithium-sulfur batteries

The sluggish conversion kinetics and shuttle effect of lithium polysulfides(LiPSs)severely hamper the commercialization of lithium-sulfur batteries.Numerous electrocatalysts have been used to address these issues,amongst which,transition metal dichalcogenides have shown excellent catalytic performance in the study of lithium-sulfur batteries.Note that dichalcogenides in different phases have different catalytic properties,and such catalytic materials in different phases have a prominent impact on the performance of lithium-sulfur batteries.Herein,1T-phase rich MoSe_(2)(T-MoSe_(2))nanosheets are synthesized and used to catalyze the conversion of LiPSs.Compared with the 2H-phase rich MoSe_(2)(H-MoSe_(2))nanosheets,the T-MoSe_(2) nanosheets significantly accelerate the liquid phase transformation of LiPSs and the nucleation process of Li2S.In-situ Raman and X-ray photoelectron spectroscopy(XPS)find that T-MoSe_(2) effectively captures LiPSs through the formation of Mo-S and Li-Se bonds,and simultaneously achieves fast catalytic conversion of LiPSs.The lithium-sulfur batteries with T-MoSe_(2) functionalized separators display a fantastic rate performance of 770.1 mAh/g at 3 C and wonderful cycling stability,with a capacity decay rate as low as 0.065%during 400 cycles at 1 C.This work offers a novel perspective for the rational design of selenide electrocatalysts in lithium-sulfur chemistry.

Fluorination Intensifying Oxygen Evolution Reaction for High-Temperature Steam Electrolysis

Solid oxide electrolysis cells(SOECs)have emerged as one of the most potent techniques for hydrogen production.As the restricted step for SOEC,as well as the most predominant obstacle to the scaled application,oxygen evolution reaction(OER)should be urgently accelerated by developing potent electrocatalysts.Despite inferior electrochemical activity to cobalt-based materials,perovskite ferrites exhibit great potential in the future with regard to good intrinsic stability and durability,abundant reserves,and good compatibility with other SOEC components.In this work,fluorination is introduced to the typical perovskite ferrite to further intensify the OER process.Ab initio calculations combined with physical-chemical characterizations are performed to reveal the mechanism.The doped F^(−)leads to debilitating the strength of the metal-oxygen bond and then reduces the energy for oxygen vacancy formation and ion migration,which renders improvements to sub-processes of OER on the anode.The well-verified material,PrBaFe_(2)O_(5+δ)F_(0.1)(PBFOF),exhibited a low polarization resistance of 0.058Ωcm^(-2).Single cells based on PBFOF showed a high current density of 2.28 A cm^(-2) at 750°C under 1.3 V.This work provides a clear insight into the mechanism of fluorination on perovskites and high-activity anode material for SOEC.

Balancing particle properties for practical lithium-ion batteries

As a state-of-the-art secondary battery,lithium-ion batteries(LIBs)have dominated the consumer electronics market since Sony unveiled the commercial secondary battery with LiCoO_(2) as the negative electrode material in the early 1990s.The key to the efficient operation of LIBs lies in the effective contact between the Li-ion-rich electrolyte and the active material particles in the electrode.The particle properties of the electrode materials affect the lithium ion diffusion path,diffusion resistance,contact area with the active material,the electrochemical performance and the energy density of batteries.To achieve satisfied comprehensive performance and of LIBs,it is not only necessary to focus on the modification of materials,but also to balance the properties of electrode material particles.Therefore,in this review,we analyze the influence of particle properties on the battery performance from three perspectives:particle size,particle size distribution,and particle shape.A deep understanding of the effect and mechanism of particles on electrodes and batteries will help develop and manufacture practical LIBs.

氧化铝载体改性及其应用研究进展

氧化铝不仅价格低廉、易获取,且具有多孔性、大比表面积、高分散性、高热稳定性等优点,常用作催化剂载体,广泛应用于工业催化领域。氧化铝的孔结构对工业催化剂性能影响很大。为优化氧化铝载体的性能,对氧化铝的扩孔和添加助剂改性已进行了大量研究。扩孔改性可降低扩散阻力并改善传质、提高活性位点的有效利用率、增强抗结焦性能,进而提高加氢催化的产率;添加助剂改性可有效抑制氧化铝载体高温烧结和相变,防止孔结构被破坏,提高催化剂的寿命。本工作介绍了制备氧化铝的方法-拟薄水铝石脱水法和溶胶-凝胶法,综述了氧化铝的扩孔方法,总结了改性氧化铝载体的最新研究进展,包括自组装法、水热处理法、扩孔剂法;阐述了氧化铝添加助剂的改性方法,包括加入稀土金属氧化物、碱(土)金属氧化物、其它金属氧化物及非金属氧化物。最后,展望了氧化铝未来的研究和发展方向。