Exploring the Core-shell Structure of BaTiO3-based Dielectric Ceramics Using Machine Learning Models and Interpretability Analysis

A machine learning(ML)-based random forest(RF)classification model algorithm was employed to investigate the main factors affecting the formation of the core-shell structure of BaTiO_(3)-based ceramics and their interpretability was analyzed by using Shapley additive explanations(SHAP).An F1-score changed from 0.8795 to 0.9310,accuracy from 0.8450 to 0.9070,precision from 0.8714 to 0.9000,recall from 0.8929 to 0.9643,and ROC/AUC value of 0.97±0.03 was achieved by the RF classification with the optimal set of features containing only 5 features,demonstrating the high accuracy of our model and its high robustness.During the interpretability analysis of the model,it was found that the electronegativity,melting point,and sintering temperature of the dopant contribute highly to the formation of the core-shell structure,and based on these characteristics,specific ranges were delineated and twelve elements were finally obtained that met all the requirements,namely Si,Sc,Mn,Fe,Co,Ni,Pd,Er,Tm,Lu,Pa,and Cm.In the process of exploring the structure of the core-shell,the doping elements can be effectively localized to be selected by choosing the range of features.

Design Engineering,Synthesis Protocols,and Energy Applications of MOF-Derived Electrocatalysts

The core reactions for fuel cells,rechargeable metal-air batteries,and hydrogen fuel production are the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER),which are heavily dependent on the efficiency of electrocatalysts.Enormous attempts have previously been devoted in non-noble electrocatalysts born out of metal-organic frameworks(MOFs)for ORR,OER,and HER applications,due to the following advantageous reasons:(i)The significant porosity eases the electrolyte diffusion;(ii)the supreme catalyst-electrolyte contact area enhances the diffusion efficiency;and(iii)the electronic conductivity can be extensively increased owing to the unique construction block subunits for MOFs-derived electrocatalysis.Herein,the recent progress of MOFs-derived electrocatalysts including synthesis protocols,design engineering,DFT calculations roles,and energy applications is discussed and reviewed.It can be concluded that the elevated ORR,OER,and HER performances are attributed to an advantageously well-designed high-porosity structure,significant surface area,and plentiful active centers.Furthermore,the perspectives of MOF-derived electrocatalysts for the ORR,OER,and HER are presented.

Improving Cyclic Stability and Rate Performance of Lithium Ion Batteries Using La^(3+)Modified LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)Cathode Materials

La_(4)NiLiO_(8)-coated NCM622 samples were prepared through a sol-gel method,and the electrochemical performance as cathode materials was investigated.It is revealed that part of the introduced La^(3+)ions produce a coating layer on the surface of NCM622 particles,while the rest occupy the 3b position of the lattice.The optimized sample exhibits a capacity retention of 96.54%after 100 cycles under 1C rate with a discharge specific capacity of 117.54 mAh·g^(-1)under 5C rate,much higher than those of the unmodified sample.The results show that the addition of La^(3+)ion can greatly improve the cyclic stability and the rate performance of NCM622.

Preparation of Co/CoOx Derived from a Lowtemperature Etching of ZIF-67 for Oxygen Reduction and Oxygen Evolution Catalytic Reaction

Catalysts consisting of Zeolite imidazolyl ester skeleton-67(ZIF-67)and graphene oxide(GO)were fabricated through a solvothermal method,followed by etching ZIF-67 with oxygen-rich functional groups on GO in a reduction atmosphere at 400℃.During this process,an open type of cobalt metal center was formed by the partial vaporization and oxidation of ZIF-67,further reducing to Co and partially combining with oxygen species to amorphous CoOx.Benefiting from the rich functional N,and metal/oxides active centers derived from the calcination process,the synthesized Co/CoOx@NSG-400 showed a low OER overpotential of 10 mA·cm^(-2) at 298 mV,and an ORR half-wave potential of 0.8 V,which demonstrated its excellent bifunctional catalytic activity.Such a controllable calcination strategy with high yields could be expected to pave the way for synthesizing low-cost and efficient bifunctional electrocatalysts.

Structural properties and electrochemical performance of different polymorphs of Nb_(2)O_(5) in magnesium-based batteries

The selection of the most suitable crystal structure for ions storage and the investigation of the corresponding reaction mechanism is still an ongoing challenge for the development of Mg-based batteries.In this article,high flexible graphene network supporting different crystal structures of Nb2 O5(TTNb_(2)O_(5)@rGO and T-Nb_(2)O_(5)@rGO) are successfully synthesized by a spray-drying-assisted approach.The three-dimensional graphene framework provides high conductivity and avoids the aggregation of Nb2 O5 nanoparticles.When employed as electrode materials for energy storage applications,TT-Nb_(2)O_(5) delivers a higher discharge capacity of 129.5 mAh g^(-1), about twice that of T-Nb_(2)O_(5) for Mg-storage,whereas,T-Nb_(2)O_(5) delivers a much higher capacity(162 mAh g^(-1)) compared with TT-Nb_(2)O_(5)(129 mAh g^(-1)) for Li-storage.Detailed investigations reveal the Mg intercalation mechanism and lower Mg^(2+) migration barriers,faster Mg^(2+) diffusion kinetics of TT-Nb_(2)O_(5) as cathode material for Mg-storage,and the faster Li+ diffusion kinetics,shorter diffusion distance of T-Nb_(2)O_(5) as cathode material for Li-storage.Our work demonstrates that exploring the proper crystal structure of Nb2 O5 for different ions storage is necessary.

Epitaxially Grown Ru Clusters-Nickel Nitride Heterostructure Advances Water Electrolysis Kinetics in Alkaline and Seawater Media

The epitaxial heterostructure can be rationally designed based on the in situ growth of two compatible phases with lattice similarity,in which the modulated electronic states and tuned adsorption behaviors are conducive to the enhancement of electrocatalytic activity.Herein,theoretical simulations first disclose the charge transfer trend and reinforced inherent electron conduction around the epitaxial heterointerface between Ru clusters and Ni_(3)N substrate(cRu-Ni_(3)N),thus leading to the optimized adsorption behaviors and reduced activation energy barriers.Subsequently,the defectrich nanosheets with the epitaxially grown cRu-Ni_(3)N heterointerface are successfully constructed.Impressively,by virtue of the superiority of intrinsic activity and reaction kinetics,such unique epitaxial heterostructure exhibits remarkable bifunctional catalytic activity toward electrocatalytic OER(226 mV@20 mA cm^(−2))and HER(32 mV@10 mA cm^(−2))in alkaline media.Furthermore,it also shows great application prospect in alkaline freshwater and seawater splitting,as well as solar-to-hydrogen integrated system.This work could provide beneficial enlightenment for the establishment of advanced electrocatalysts with epitaxial heterointerfaces.

Awakening the oxygen evolution activity of MoS_(2) by oxophilic-metal induced surface reorganization engineering

Although molybdenum disulfide (MoS_(2))-based materials are generally known as active electrocatalysts for the hydrogen evolution reaction (HER), the inert performance for the oxygen evolution reaction (OER) seriously limits their wide applications in alkaline electrolyzers due to there exists too strong metal-sulfur (M−S) bond in MoS_(2). Herein, by means of surface reorganization engineering of bimetal Al, Co-doped MoS_(2) (devoted as AlCo_(3)-MoS_(2)) through in situ substituting partial oxidation, we successfully significantly activate the OER activity of MoS_(2), which affords a considerably low overpotential of 323 mV at −30 mA cm^(−2), far lower than those of MoS_(2), Al-MoS_(2) and Co-MoS_(2) catalysts. Essentially, the AlCo_(3)-MoS_(2) substrate produces lots of M−O (M=Al, Co and Mo) species with oxygen vacancies, which trigger the surface self-reconstruction of pre-catalysts and simultaneously boost the electrocatalytic OER activity. Moreover, benefiting from the moderate M−O species formed on the surface, the redistribution of surface electron states is induced, thus optimizing the adsorption of OH* and OOH* intermediates on metal oxyhydroxides and awakening the OER activity of MoS_(2).

Defect engineering of high-loading single-atom catalysts for electrochemical carbon dioxide reduction

Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides an attractive approach to carbon capture and utilization for the production high-value-added products.However,CO_(2)RR still suffers from poor selectivity and low current density due to its sluggish kinetics and multitudinous reaction pathways.Single-atom catalysts(SACs)demonstrate outstanding activity,excellent selectivity,and remarkable atom utilization efficiency,which give impetus to the search for electrocatalytic processes aiming at high selectivity.There appears significant activity in the development of efficient SACs for CO_(2)RR,while the density of the atomic sites remains a considerable barrier to be overcome.To construct high-metal-loading SACs,aggregation must be prevented,and thus novel strategies are required.The key to creating high-density atomically dispersed sites is designing enough anchoring sites,normally defects,to stabilize the highly mobile separated metal atoms.In this review,we summarized the advances in developing high-loading SACs through defect engineering,with a focus on the synthesis strategies to achieve high atomic site loading.Finally,the future opportunities and challenges for CO_(2)RR in the area of high-loading single-atom electrocatalysts are also discussed.

On-site conversion reaction enables ion-conducting surface on red phosphorus/carbon anode for durable and fast sodium-ion batteries

The practical applications of high-capacity alloy-type anode materials in sodium-ion batteries(SIBs)are challenged by their vast volume effects and resulting unstable electrode-electrolyte interphases during discharge-charge cycling.Taking red phosphorus(P)/carbon anode material as an example,we report an on-site conversion reaction to intentionally eliminate the volume effect-dominated surface P and yield an ionically conducting layer of Na3PS4solid-state electrolyte on the composite.Such a surface reconstruction can significantly suppress the electrode swelling and simultaneously enable the activation energy of interfacial Na+transfer as low as 36.7 k J mol^(-1),resulting in excellent electrode stability and ultrafast reaction kinetics.Consequently,excellent cycling performance(510 mA h g^(-1)at 5 A g^(-1)after 1000 cycles with a tiny capacity fading rate of 0.016%per cycle)and outstanding rate capability(484 mA h g^(-1)at 10 A g^(-1)are achieved in half cells.When coupled with Na_(3)V_(2)(PO4)3cathode,the full cells exhibit 100%capacity retention over 200 cycles at 5C with an average Coulombic efficiency of 99.93%and a high energy density of 125.5 W h kg^(-1)at a power density of 8215.6 W kg^(-1)(charge or discharge within~49 s).Remarkably,the full cell can steadily operate at a high areal capacity of 1.9 mA h cm^(-2),the highest level among red P-based full SIBs ever reported.

Anomalous Hall effect in ferromagnetic LaCo_(2)As_(2) and ferrimagnetic NdCo_(2)As_(2)

We conducted a comparative study of the magnetic and transport properties of single-crystalline LaCo_(2)As_(2) and NdCo_(2)As_(2).LaCo_(2)As_(2) is a soft metallic ferromagnet which exhibits purely intrinsic anomalous Hall effect(AHE) due to Co-3d electrons. With Nd-4f electronic magnetism, ferrimagnetic NdCo_(2)As_(2) manifests pronounced sign reversal and multiple hysteresis loops in temperature-and field-dependent magnetization, Hall resistivity, and magnetoresistance, due to complicated magnetic structural changes. We reveal that the AHE for NdCo_(2)As_(2) is stemming from the Co sub-lattice and deduce its phase diagram which includes magnetic compensation and two meta-magnetic phase transitions. The sensitivity of the Hall effect on the details of the magnetic structures in ferrimagnetic NdCo_(2)As_(2) provides a unique opportunity to explore the magnetic interaction between 4f and 3d electrons and its impact on the electronic structure.

Mitigating the dissolution of V_(2)O_(5) in aqueous ZnSO_(4) electrolyte through Ti-doping for zinc storage

Aqueous zinc-ion batteries(AZIBs)have become a hotspot for electrochemical energy storage owing to the high safety,low cost,environmental friendliness,and favorable rate performance.However,the serious dissolution of cathode materials in aqueous electrolytes would lead to poor cyclability,which should be addressed before commercialization.Herein,we designed a Ti-doped V_(2)O_(5) with yolk-shell microspherical structure for AZIBs.The Ti doping stabilizes the crystal structure and relieves the dissolution of V_(2)O_(5) in aqueous ZnSO_(4) electrolyte.The optimized sample,Ti_(0.2)V_(1.8)O_(4.9),delivers a high capacity(355 mAh/g at 0.05 A/g)as well as good capacity retention(89%after 2500 cycles at 1.0 A/g).This work provides an effective strategy to mitigate the dissolution of cathode material in aqueous ZnSO_(4) electrolyte for cyclability enhancement.

Defect and Doping Co‑Engineered Non‑Metal Nanocarbon ORR Electrocatalyst

Exploring low-cost and earth-abundant oxygen reduction reaction(ORR)electrocatalyst is essential for fuel cells and metal–air batteries.Among them,non-metal nanocarbon with multiple advantages of low cost,abundance,high conductivity,good durability,and competitive activity has attracted intense interest in recent years.The enhanced ORR activities of the nanocarbons are normally thought to originate from heteroatom(e.g.,N,B,P,or S)doping or various induced defects.However,in practice,carbon-based materials usually contain both dopants and defects.In this regard,in terms of the co-engineering of heteroatom doping and defect inducing,we present an overview of recent advances in developing non-metal carbon-based electrocatalysts for the ORR.The characteristics,ORR performance,and the related mechanism of these functionalized nanocarbons by heteroatom doping,defect inducing,and in particular their synergistic promotion effect are emphatically analyzed and discussed.Finally,the current issues and perspectives in developing carbon-based electrocatalysts from both of heteroatom doping and defect engineering are proposed.This review will be beneficial for the rational design and manufacturing of highly efficient carbon-based materials for electrocatalysis.

Rechargeable metal(Li, Na, Mg, Al)-sulfur batteries: Materials and advances

Energy and environmental issues are becoming more and more severe and renewable energy storage technologies are vital to solve the problem.Rechargeable metal(Li,Na,Mg,Al)-sulfur batteries with low-cost and earth-abundant elemental sulfur as the cathode are attracting more and more interest for electrical energy storage in recent years.Lithium-sulfur(Li-S),room-temperature sodium-sulfur(RT Na-S),magnesium-sulfur(Mg-S)and aluminum-sulfur(Al-S)batteries are the most prominent candidates among them.Many obvious obstacles are hampering the developments of metal-sulfur batteries.Li-S and Na-S batteries are encumbered mainly by anode dendrite issues,polysulfides shuttle and low conductivity of cathodes.Mg-S and Al-S batteries are short of suitable electrolytes.In this review,relationships between various employed nanostructured materials and electrochemical performances of metal-sulfur batteries have been demonstrated.Moreover,the selections of suitable electrolytes,anode protection,separator modifications and prototype innovations are all crucial to the developments of metal-sulfur batteries and are discussed at the same time.Herein,we give a review on the advances of Li-S,RT Na-S,Mg-S and Al-S batteries from the point of view of materials,and then focus on perspectives of their future developments.

Surface pseudocapacitance of mesoporous Mo_(3)N_(2) nanowire anode toward reversible high-rate sodium-ion storage

Sodium-ion storage devices are highly desirable for large-scale energy storage applications owing to the wide availability of sodium resources and low cost.Transition metal nitrides(TMNs)are promising anode materials for sodium-ion storage,while their detailed reaction mechanism remains unexplored.Herein,we synthesize the mesoporous Mo3N2 nanowires(Meso-Mo_(3)N_(2)-NWs).The sodium-ion storage mechanism of Mo3N2 is systematically investigated through in-situ XRD,ex-situ experimental characterizations and detailed kinetics analysis.Briefly,the Mo_(3)N_(2) undergoes a surface pseudocapacitive redox charge storage process.Benefiting from the rapid surface redox reaction,the Meso-Mo_(3)N_(2)-NWs anode delivers high specific capacity(282 m Ah g^(-1) at 0.1 A g^(-1)),excellent rate capability(87 m Ah g^(-1) at 16 A g^(-1))and long cycling stability(a capacity retention of 78.6%after 800 cycles at 1 A g^(-1)).The present work highlights that the surface pseudocapacitive sodium-ion storage mechanism enables to overcome the sluggish sodium-ion diffusion process,which opens a new direction to design and synthesize high-rate sodiumion storage materials.

Ultra-small platinum nanoparticles segregated by nickle sites for efficient ORR and HER processes

In the electrochemical process,Pt nanoparticles(NPs)in Pt-based catalysts usually agglomerate due to Oswald ripening or lack of restraint,ultimately resulting in reduction of the active sites and catalytic efficiency.How to uniformly disperse and firmly fix Pt NPs on carbon matrix with suitable particle size for catalysis is still a big challenge.Herein,to prevent the agglomeration and shedding of Pt NPs,Ni species is introduced and are evenly dispersed in the surface of carbon matrix in the form of Ni-N-C active sites(Ni ZIF-NC).The Ni sites can be used to anchor Pt NPs,and then effectively limit the further growth and agglomeration of Pt NPs during the reaction process.Compared with commercial Pt/C catalyst,Pt@Ni ZIF-NC,with ultralow Pt loading(7 wt%)and ideal particle size(2.3 nm),not only increases the active center,but also promotes the catalysis kinetics,greatly improving the ORR and HER catalytic activity.Under acidic conditions,its half-wave potential(0.902 V)is superior to commercial Pt/C(0.861 V),and the mass activity(0.38 A per mg Pt)at 0.9 V is 4.7 times that of Pt/C(0.08 A per mg Pt).Besides,it also shows outstanding HER performance.At 20 and 30 mV,its mass activity is even 2 and 6 times that of Pt/C,respectively.Whether it is under ORR or HER conditions,it still shows excellent durability.These undoubtedly indicate the realization of dual-functional catalysts with low-Pt and high-efficiency properties.

Sulfur-linked carbonyl polymer as a robust organic cathode for rapid and durable aluminum batteries

Rechargeable aluminum batteries are believed as a promising next-generation energy-storage system due to abundant low-cost Al sources and high volumetric specific capacity.The Al-storage cathodes,however,are plagued by strong electrostatic interaction between host materials and carrier ions,leading to large overpotential and undesired cycling stability as well as sluggish ion diffusion kinetics.Herein,sulfur-linked carbonyl polymer based on perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA) as the cathode materials for ABs is proposed,which demonstrates a small voltage polarization(135 mV),a reversible capacity of 110 mAh g^(-1) at 100 mA g^(-1) even after 1200 cycles,and rapid Al-storage kinetics.Compared with PTCDA,the sulfide polymer possesses higher working voltage because of its lower LUMO energy level according to theoretical calculation.The ordered carbonyl active sites in sulfide polymer contribute to the maximized material utilization and rapid ion coordination and dissociation,resulting in superior rate capability.Besides,the bridged thioether bonds endow the polysulfide with robust and flexible structure,which inhibits the dissolution of active materials and improves cycling stability.This work implies the importance of ordered arrangement of redox active moieties for organic electrode,which provides the theoretical direction for the structural design of organic materials applied in multivalent-ion batteries.

Groups-dependent phosphines as the organic redox for point defects elimination in hybrid perovskite solar cells

Lead(Pb)^(0) and iodine(I)^(0) point defects generated during perovskite solar cell(PSC)fabrication and photoconversion form deep band energy levels as the carriers’recombination centers.These defects not only deteriorate device efficiency,but also facilitate chemical degradation with ion migration,resulting in restricted device lifetime.Herein,we present a novel type of phosphines as the point defects stabilizer for hybrid perovskite solar cells with enhanced performances.Three phosphines with varied side groups of tributyl,trioctyl and triphenyl are exampled as the dopants in perovskite films.The group dependent redox properties were observed in the perovskite film,dependent on their molecular weights and steric hinderances of phosphines.The partially oxidized tributyl phosphine(TBUP)with additional tributyl phosphine oxides(TBPO)is efficient in reduction of lead(Pb)^(0) and iodine(I)^(0) concentrations during the device fabrication and operation.The device with TBUP-TBPO pair showed enhanced power conversion efficiency(PCE)to 20.48% and maintain 91.7% of their initial PCEs after 500 h at 65℃ thermal annealing.Thus,this work presents an efficient route of utilize the phosphine species to reduce point defects in the perovskite film,which promoting further development of novel phosphorous additives with defects stabilization,interface passivation and encapsulation for low-cost solution processed PSCs.

Pancake-Like MOF Solid-State Electrolytes with Fast Ion Migration for High-Performance Sodium Battery

Solid-state electrolyte(SSE)of the sodium-ion battery have attracted tremendous attention in the next generation energy storage materials on account of their wide electrochemical window and thermal stability.However,the high interfacial impedance,low ion transference number and complex preparation process restrict the application of SSE.Herein,inspired by the excellent sieving function and high specific surface area of red blood cells,we obtained a solid-like electrolyte(SLE)based on the combination of the pancake-like metal-organic framework(MOF)with liquid electrolyte,possessing a high ionic conductivity of 6.60×10^(-4) S cm^(−1),and excellent sodium metal compatibility.In addition,we investigated the ion restriction effect of MOF’s apertures size and special functional groups,and the ion transference number increased from 0.16 to 0.33.Finally,the assembled Na_(0.44)MnO_(2)//SLE//Na full batteries showed no obvious capacity decrease after 160 cycles.This material design of SLE in our work is an important key to obtain fast ion migration SLE for high-performance sodium-ion batteries.

A critical review of key materials and issues in solid oxide cells

Solid oxide cells(SOCs)are all solid ceramic devices with the dual functionality of solid oxide fuel cells(SOFCs)to convert the chemical energy of fuels like H2,natural gas and other hydrocarbons to electricity and of solid oxide electrolysis cells(SOECs)to store renewable electric energy of sun and wind in hydrogen fuel.Among the electrochemical energy conversion and storage devices,SOCs are the most clean and efficient technology with unique dual functionality.Due to the high operation temperature(typically 600–800°C),SOCs exhibit many advantages over other energy conversion devices,such as low material cost,high efficiency and fuel flexibility.There has been rapid development of SOC technologies over the last decade with significant advantages and progress in key materials and a fundamental understanding of key issues such as an electrode,electrolyte,performance degradation,poisoning,and stack design.The reversible polarization also has a critical effect on the surface segregation and stability of the electrode and electrode/electrolyte interface.This critical review starts with a brief introduction,working principles and thermodynamics of SOC technology to readers with interests in this rapidly developing and emerging field.Then the key materials currently used in SOCs are summarized,followed by the discussion of the most advanced electrode modification methods and critical issues of SOCs,including the surface chemistry,segregation,electrode/electrolyte interface and varying material degradation mechanisms under reversible operations.The challenges and prospects of SOC technology for future developments are discussed.

Low-cost biodegradable lead sequestration film for perovskite solar cells

Despite the high efficiency that has been achieved for the perovskite solar cells(PSCs),the hazardous lead leakage from the perovskite absorber layer is one of the crucial barriers still hindering its penetration into the commercial market for a large-scale installation.Herein,we report a novel low-cost and biodegradable lead sequestration layer with high compatibility for up-scalable encapsulation of PSCs.Through a precisely designed cross-linking reaction of chemical agents,the as-made biodegradable chitosan composite film shows enhanced mechanical strength,chemical stability,and lead adsorption capacity.The designed encapsulation strategy reduces over 99.99% lead leakage to <2 ppb under varied simulations of weather conditions(hail,rain,or flood),which meet the safe level of drinking water set by the US Environmental Protection Agency(EPA).Moreover,the PSC efficiency is improved from 21.91% to22.82% due to the improved light absorption from the printed biodegradable lead absorption film.Finally,we present a prototype process of accumulation and recycling of lead compounds in PSCs derbies via the biodegradation process.Based on the low-cost biodegradable lead sequestration film,this environmental-friendly encapsulation strategy could address the lead leakage issue for further commercialization of PSCs.