With the increasing spotlight in electric vehicles,there is a growing demand for high-energy-density batteries to enhance driving range.Consequently,several studies have been conducted on high-energy-density LiNi_(x)C...With the increasing spotlight in electric vehicles,there is a growing demand for high-energy-density batteries to enhance driving range.Consequently,several studies have been conducted on high-energy-density LiNi_(x)Co_(y)Mn_(z)O_(2)cathodes.However,there is a limit to permanent performance deterioration because of side reactions caused by moisture in the atmosphere and continuous microcracks during cycling as the Ni content to express high energy increases and the content of Mn and Co that maintain structural and electrochemical stabilization decreases.The direct modification of the surface and bulk regions aims to enhance the capacity and long-term performance of high-Ni cathode materials.Therefore,an efficient modification requires a study based on a thorough understanding of the degradation mechanisms in the surface and bulk region.In this review,a comprehensive analysis of various modifications,including doping,coating,concentration gradient,and single crystals,is conducted to solve degradation issues along with an analysis of the overall degradation mechanism occurring in high-Ni cathode materials.It also summarizes recent research developments related to the following modifications,aims to provide notable points and directions for post-studies,and provides valuable references for the commercialization of stable high-energy-density cathode materials.展开更多
Recent advances in functionally graded additive manufacturing(FGAM)technology have enabled the seamless hybridization of multiple functionalities in a single structure.Soft robotics can become one of the largest benef...Recent advances in functionally graded additive manufacturing(FGAM)technology have enabled the seamless hybridization of multiple functionalities in a single structure.Soft robotics can become one of the largest beneficiaries of these advances,through the design of a facile four-dimensional(4D)FGAM process that can grant an intelligent stimuli-responsive mechanical functionality to the printed objects.Herein,we present a simple binder jetting approach for the 4D printing of functionally graded porous multi-materials(FGMM)by introducing rationally designed graded multiphase feeder beds.Compositionally graded cross-linking agents gradually form stable porous network structures within aqueous polymer particles,enabling programmable hygroscopic deformation without complex mechanical designs.Furthermore,a systematic bed design incorporating additional functional agents enables a multi-stimuli-responsive and untethered soft robot with stark stimulus selectivity.The biodegradability of the proposed 4D-printed soft robot further ensures the sustainability of our approach,with immediate degradation rates of 96.6%within 72 h.The proposed 4D printing concept for FGMMs can create new opportunities for intelligent and sustainable additive manufacturing in soft robotics.展开更多
Layered-type transition metal(TM)oxides are considered as one of the most promising cathodes for K-ion batteries because of the large theoretical gravimetric capacity by low molar mass.However,they suffer from severe ...Layered-type transition metal(TM)oxides are considered as one of the most promising cathodes for K-ion batteries because of the large theoretical gravimetric capacity by low molar mass.However,they suffer from severe structural change by de/intercalation and diffusion of K^(+)ions with large ionic size,which results in not only much lower reversible capacity than the theoretical capacity but also poor power capability.Thus,it is important to enhance the structural stability of the layered-type TM oxides for outstanding electrochemical behaviors under the K-ion battery system.Herein,it is investigated that the substitution of the appropriate Ti^(4+)contents enables a highly enlarged reversible capacity of P3-type KxCrO_(2) using combined studies of first-principles calculation and various experiments.Whereas the pristine P3-type KxCrO_(2) just exhibits the reversible capacity of∼120 mAh g^(−1) in the voltage range of 1.5-4.0 V(vs.K^(+)/K),the∼0.61 mol K^(+)corresponding to∼150 mAh g^(−1) can be reversible de/intercalated at the structure of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) under the same conditions.Furthermore,even at the high current density of 788 mA g^(−1),the specific capacity of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) is∼120 mAh g^(−1),which is∼81 times larger than that of the pristine P3-type KxCrO_(2).It is believed that this research can provide an effective strategy to improve the electrochemical performances of the cathode materials suffered by severe structural change that occurred during charge/discharge under not only K-ion battery system but also other rechargeable battery systems.展开更多
In recent years,metal halide perovskites have received significant attention as materials for next-generation optoelectronic devices owing to their excellent optoelectronic properties.The unprecedented rapid evolution...In recent years,metal halide perovskites have received significant attention as materials for next-generation optoelectronic devices owing to their excellent optoelectronic properties.The unprecedented rapid evolution in the device performance has been achieved by gaining an advanced understanding of the composition,crystal growth,and defect engineering of perovskites.As device performances approach their theoretical limits,effective optical management becomes essential for achieving higher efficiency.In this review,we discuss the status and perspectives of nano to micron-scale patterning methods for the optical management of perovskite optoelectronic devices.We initially discuss the importance of effective light harvesting and light outcoupling via optical management.Subsequently,the recent progress in various patterning/texturing techniques applied to perovskite optoelectronic devices is summarized by categorizing them into top-down and bottom-up methods.Finally,we discuss the perspectives of advanced patterning/texturing technologies for the development and commercialization of perovskite optoelectronic devices.展开更多
Lithium-sulfur batteries(LSBs)have drawn significant attention owing to their high theoretical discharge capacity and energy density.However,the dissolution of long-chain polysulfides into the electrolyte during the c...Lithium-sulfur batteries(LSBs)have drawn significant attention owing to their high theoretical discharge capacity and energy density.However,the dissolution of long-chain polysulfides into the electrolyte during the charge and discharge process(“shuttle effect”)results in fast capacity fading and inferior electrochemical performance.In this study,Mn_(2)O_(3)with an ordered mesoporous structure(OM-Mn_(2)O_(3))was designed as a cathode host for LSBs via KIT-6 hard templating,to effectively inhibit the polysulfide shuttle effect.OM-Mn_(2)O_(3)offers numerous pores to confine sulfur and tightly anchor the dissolved polysulfides through the combined effects of strong polar-polar interactions,polysulfides,and sulfur chain catenation.The OM-Mn_(2)O_(3)/S composite electrode delivered a discharge capacity of 561 mAh g^(-1) after 250 cycles at 0.5 C owing to the excellent performance of OM-Mn_(2)O_(3).Furthermore,it retained a discharge capacity of 628mA h g^(-1) even at a rate of 2 C,which was significantly higher than that of a pristine sulfur electrode(206mA h g^(-1)).These findings provide a prospective strategy for designing cathode materials for high-performance LSBs.展开更多
The anionic redox has been widely studied in layered-oxide-cathodes in attempts to achieve highenergy-density for Na-ion batteries(NIBs).It is known that an oxidation state of Mn^(4+) or Ru^(5+) is essential for the a...The anionic redox has been widely studied in layered-oxide-cathodes in attempts to achieve highenergy-density for Na-ion batteries(NIBs).It is known that an oxidation state of Mn^(4+) or Ru^(5+) is essential for the anionic reaction of O^(2-)/O~-to occur during Na^(+) de/intercalation.However,here,we report that the anionic redox can occur in Ru-based layered-oxide-cathodes before full oxidation of Ru^(4+)/Ru^(5+).Combining studies using first-principles calculation and experimental techniques reveals that further Na^(+) deintercalation from P2-Na_(0.33)[Mg_(0.33)Ru_(0.67)]O_(2) is based on anionic oxidation after 0.33 mol Na^(+) deintercalation from P2-Na_(0.67)[Mg_(0.33)Ru_(0.67)]O_(2) with cationic oxidation of Ru^(4+)/Ru^(4.5+).Especially,it is revealed that the only oxygen neighboring 2Mg/1 Ru can participate in the anionic redox during Na^(+) de/intercalation,which implies that the Na-O-Mg arrangement in the P2-Na_(0.33)[M9_(0.33)Ru_(0.67)]O_(2) structure can dramatically lower the thermodynamic stability of the anionic redox than that of cationic redox.Through the O anionic and Ru cationic reaction,P2-Na_(0.67)[Mg_(0.33)Ru_(0.67)]O_(2) exhibits not only a large specific capacity of~172 mA h g^(-1) but also excellent power-capability via facile Na^(+) diffusion and reversible structural change during charge/discharge.These findings suggest a novel strategy that can increase the activity of anionic redox by modulating the local environment around oxygen to develop high-energy-density cathode materials for NIBs.展开更多
Batteries that utilize low-cost elemental sulfur and light metallic lithium as electrodes have great potential in achieving high energy density.However,building a lithium-sulfur(Li-S)full battery by controlling the el...Batteries that utilize low-cost elemental sulfur and light metallic lithium as electrodes have great potential in achieving high energy density.However,building a lithium-sulfur(Li-S)full battery by controlling the electrolyte volume generally produces low practical energy because of the limited electrochemical Li-S redox.Herein,the high energy/high performance of a Li-S full battery with practical sulfur loading and minimum electrolyte volume is reported.A unique hybrid architecture configured with Ni-Co metal alloy(NiCo)and metal oxide(NiCoO_(2))nanoparticles heterogeneously anchored in carbon nanotube-embedded selfstanding carbon matrix is fabricated as a host for sulfur.This work demonstrates the considerable improvement that the hybrid structure's high conductivity and satisfactory porosity promote the transport of electrons and lithium ions in Li-S batteries.Through experimental and theoretical validations,the function of NiCo and NiCoO_(2) nanoparticles as an efficient polysulfide mediator is established.These particles afford polysulfide anchoring and catalytic sites for Li-S redox reaction,thus improving the redox conversion reversibility.Even at high sulfur loading,the nanostructured Ni-Co metal alloy and metal oxide enable to have stable cycling performance under lean electrolyte conditions both in half-cell and full-cell batteries using a graphite anode.展开更多
Electrochemical nitrate reduction(ENR)is an economical and eco-friendly method for converting industrial wastewater into valuable ammonia under atmospheric conditions.The main challenge lies in designing and developin...Electrochemical nitrate reduction(ENR)is an economical and eco-friendly method for converting industrial wastewater into valuable ammonia under atmospheric conditions.The main challenge lies in designing and developing highly durable ENR electrocatalysts.This study introduces defect-rich mesoporous CuO_(x) nanowires electrocatalyst synthesized using a novel solution-flame(sol-flame)hybrid method to control mesoporosity and introduce surface defects,thereby enhancing the electrochemical nitrate-toammonia production performance.We found surface defects(oxygen vacancies and Cu^(+))and unique mesoporous nanowire structure composed of tightly interconnected nanoparticles.The sol-flamesynthesized CuO_(x) nanowires(sf-CuO NWs)achieved superior ammonia yield rate(0.51 mmol h^(-1)cm^(-2)),faradaic efficiency(97.3%),and selectivity(86.2%)in 1 M KOH electrolyte(2000 ppm nitrate).This performance surpasses that of non-porous and less-defective CuO NWs and is attributed to the increased surface area and rapid electron transport facilitated by the distinctive morphology and generated defects.Theoretical calculation further suggests oxygen vacancies enhance NO_(3)^(-)adsorption on the sf-CuO NWs’surface and mitigate the competing hydrogen evolution reaction.This study outlines a strategic design and simple synthesis approach for nanowire electrocatalysts that boost the efficiency of electrochemical nitrate-to-ammonia conversion.展开更多
The polymeric gel electrolytes are attractive owing to their higher ionic conductivities than those of dry polymer electrolytes and lowered water activity for enlarged potential window.However,the ionic conductivity a...The polymeric gel electrolytes are attractive owing to their higher ionic conductivities than those of dry polymer electrolytes and lowered water activity for enlarged potential window.However,the ionic conductivity and mechanical strength of the Na-ion conducting polymeric gel electrolytes are limited by below 20 mS cm−1 and 2.2 MPa.Herein,we demonstrate Na-ion conducting and flexible polymeric hydrogel electrolytes of the chemically coupled poly(diallyldimethylammonium chloride)-dextrin-N,N′-methylene-bisacrylamide film immersed in NaClO_(4) solution(ex-DDA-Dex+NaClO_(4))for flexible sodium-ion hybrid capacitors(f-NIHC).In particular,the anion exchange reaction and synergistic interaction of ex-DDA-Dex with the optimum ClO_(4)−enable to greatly improve the ionic conductivity up to 27.63 mS cm−1 at 25◦C and electrochemical stability window up to 2.6 V,whereas the double networking structure leads to achieve both the mechanical strength(7.48 MPa)and softness of hydrogel electrolytes.Therefore,the f-NIHCs with the ex-DDA-Dex+NaClO_(4) achieved high specific and high-rate capacities of 192.04 F g^(−1)at 500 mA g^(−1)and 116.06 F g^(−1)at 10000 mA g^(−1),respectively,delivering a large energy density of 120.03Wh kg^(−1)at 906Wkg^(−1)and long cyclability of 70%over 500 cycles as well as demonstrating functional operation under mechanical stresses.展开更多
Si is considered as the promising anode materials for lithium-ion batteries(LIBs)owing to their high capacities of 4200 mAh g-1and natural abundancy.However,severe electrode pulverization and poor electronic and Li-io...Si is considered as the promising anode materials for lithium-ion batteries(LIBs)owing to their high capacities of 4200 mAh g-1and natural abundancy.However,severe electrode pulverization and poor electronic and Li-ionic conductivities hinder their practical applications.To resolve the afore-mentioned problems,we first demonstrate a cation-mixed disordered lattice and unique Li storage mechanism of single-phase ternary GaSiP_(2)compound,where the liquid metallic Ga and highly reactive P are incorporated into Si through a ball milling method.As confirmed by experimental and theoretical analyses,the introduced Ga and P enables to achieve the stronger resistance against volume variation and metallic conductivity,respectively,while the cation-mixed lattice provides the faster Li-ionic diffusion capability than those of the parent GaP and Si phases.The resulting GaSiP_(2)electrodes delivered the high specific capacity of 1615 mAh g-1and high initial Coulombic efficiency of 91%,while the graphite-modified GaSiP_(2)(GaSiP_(2)@C)achieved 83%of capacity retention after 900 cycles and high-rate capacity of 800 at 10,000 mA g-1.Furthermore,the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)//Ga SiP_(2)@C full cells achieved the high specific capacity of 1049 mAh g-1after 100 cycles,paving a way for the rational design of high-performance LIB anode materials.展开更多
Sluggish oxygen reduction reaction(ORR)kinetics are a major obstacle to developing intermediate-temperature solid-oxide fuel cells(IT-SOFCs).In particular,engineering the anion defect concentration at an interface bet...Sluggish oxygen reduction reaction(ORR)kinetics are a major obstacle to developing intermediate-temperature solid-oxide fuel cells(IT-SOFCs).In particular,engineering the anion defect concentration at an interface between the cathode and electrolyte is important for facilitating ORR kinetics and hence improving the electrochemical performance.We developed the yttria-stabilized zirconia(YSZ)nanofiber(NF)-based composite cathode,where the oxygen vacancy concentration is controlled by varying the dopant cation(Y2O3)ratio in the YSZ NFs.The composite cathode with the optimized oxygen vacancy concentration exhibits maximum power densities of 2.66 and 1.51 W cm^(−2)at 700 and 600℃,respectively,with excellent thermal stability at 700℃ over 500 h under 1.0 A cm^(−2).Electrochemical impedance spectroscopy and distribution of relaxation time analysis revealed that the high oxygen vacancy concentration in the NF-based scaffold facilitates the charge transfer and incorporation reaction occurred at the interfaces between the cathode and electrolyte.Our results demonstrate the high feasibility and potential of interface engineering for achieving IT-SOFCs with higher performance and stability.展开更多
Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions dur...Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions during anionic redox reactions lead to poor electrochemical performance with sluggish kinetics.Here, we propose a synergy of Li-Cu cations in harnessing the full potential of oxygen redox, through Li displacement and suppressed phase transition in P3-type layered oxide cathode. P3-type Na_(0.7)[Li_(0.1)Cu_(0.2)Mn_(0.7)]O_(2) cathode delivers a large specific capacity of ~212 mA h g^(-1)at 15 mA g^(-1). The discharge capacity is maintained up to ~90% of the initial capacity after 100 cycles, with stable occurrence of the oxygen redox in the high-voltage region. Through advanced experimental analyses and first-principles calculations, it is confirmed that a stepwise redox reaction based on Cu and O ions occurs for the charge-compensation mechanism upon charging. Based on a concrete understanding of the reaction mechanism, the Li displacement by the synergy of Li-Cu cations plays a crucial role in suppressing the structural change of the P3-type layered material under the oxygen redox reaction, and it is expected to be an effective strategy for stabilizing the oxygen redox in the layered oxides of Na-ion batteries.展开更多
Lithium-oxygen(Li-O_(2))batteries are an emerging energy storage alternative with the potential to meet the recent increase in demand for high-energy-density batteries.From a practical viewpoint,lithium-air(Li-Air)bat...Lithium-oxygen(Li-O_(2))batteries are an emerging energy storage alternative with the potential to meet the recent increase in demand for high-energy-density batteries.From a practical viewpoint,lithium-air(Li-Air)batteries using ambient air instead of pure oxygen could be the final goal.However,the slow oxygen reduction and evolution reactions interfere with reversible cell operation during cycling.Therefore,research continues to explore various catalyst materials.The present study attempts to improve the performance of Li-Air batteries by using porphyrin-based materials known to have catalytic effects in Li-O_(2) batteries.The results confirm that the iron phthalocyanine(FePc)catalyst not only exhibits a catalytic effect in an air atmosphere with a low oxygen fraction but also suppresses electrolyte decomposition by stabilizing superoxide radical ions(O_(2)^(−))at a high voltage range.Density functional theory calculations are used to gain insight into the exact FePc-mediated catalytic mechanism in Li-Air batteries,and various ex situ and in situ analyses reveal the reversible reactions and structural changes in FePc during electrochemical reaction.This study provides a practical solution to ultimately realize an air-breathing battery using nature-friendly catalyst materials.展开更多
Perovskite solar cells(PSCs)have developed rapidly,positioning them as potential candidates for nextgeneration renewable energy sources.However,conventional trial-and-error approaches and the vast compositional parame...Perovskite solar cells(PSCs)have developed rapidly,positioning them as potential candidates for nextgeneration renewable energy sources.However,conventional trial-and-error approaches and the vast compositional parameter space continue to pose challenges in the pursuit of exceptional performance and high stability of perovskite-based optoelectronics.The increasing demand for novel materials in optoelectronic devices and establishment of substantial databases has enabled data-driven machinelearning(ML)approaches to swiftly advance in the materials field.This review succinctly outlines the fundamental ML procedures,techniques,and recent breakthroughs,particularly in predicting the physical characteristics of perovskite materials.Moreover,it highlights research endeavors aimed at optimizing and screening materials to enhance the efficiency and stability of PSCs.Additionally,this review highlights recent efforts in using characterization data for ML,exploring their correlations with material properties and device performance,which are actively being researched,but they have yet to receive significant attention.Lastly,we provide future perspectives,such as leveraging Large Language Models(LLMs)and text-mining,to expedite the discovery of novel perovskite materials and expand their utilization across various optoelectronic fields.展开更多
Perovskite solar cells(PSCs)have shown remarkable advancements and achieved impressive power conversion efficiencies since their initial introduction in 2012.However,challenges regarding stability,quality,and sustaina...Perovskite solar cells(PSCs)have shown remarkable advancements and achieved impressive power conversion efficiencies since their initial introduction in 2012.However,challenges regarding stability,quality,and sustainability must be addressed for their successful commercial use.This review analyses the recent studies and challenges related to the operating life and end-of-life utilization of PSCs.Strategies to enhance the stability and mitigate the toxic Pb leakage in operational and recycling approaches of discarded PSCs post their end-of-life are examined to establish a viable and sustainable PSC industry.Additionally,future research directions are proposed for the advancements in the PSC industry.The goal is to ensure high efficiency as well as economic and environmental sustainability throughout the lifecycle of PSCs.展开更多
Dual ion storage hybrid supercapacitors(HsCs)are considered as a promising device to overcome the limited energy density of existing supercapacitors while preserving high power and long cyclability.However,the develop...Dual ion storage hybrid supercapacitors(HsCs)are considered as a promising device to overcome the limited energy density of existing supercapacitors while preserving high power and long cyclability.However,the development of high-capacity anion-storing materials,which can be paired with fast charg-ing capacitive electrodes,lags behind cation-storing counterparts.Herein,we demonstrate the surface faradaic OH-storage mechanism of anion storing perovskite oxide composites and their application in high-performance dual ion HsCs.The oxygen vacancy and nanoparticle size of the reduced LaMnO_(3)(r-LaMnO_(3))were controlled,while r-LaMnO_(3) was chemically coupled with ozonated carbon nanotubes(oCNTs)for the improved anion storing capacity and cycle performance.As taken by in-situ and ex-situ spectroscopic and computational analyses,OH-ions are inserted into the oxygen vacancies coordi-nating with octahedral Mn with the increase in the oxidation state of Mn during the charging process or vice versa.Configuring OH-storing r-LaMnO_(3)/oCNT composite with Na*storing MXene,the as-fabricated aqueous dual ion HSCs achieved the cycle performance of 73.3%over 10,000 cycles,delivering the max-imum energy and power densities of 47.5 w h kg^(-1) and 8 kw kg^(-1),respectively,far exceeding those of previously reported aqueous anion and dual ion storage cells.This research establishes a foundation for the unique anion storage mechanism of the defect engineered perovskite oxides and the advancement of dual ion hybrid energy storage devices with high energy and power densities.展开更多
Magnesium-ion batteries(MIBs)have promising applications because of their high theoretical capacity and the natural abundance of magnesium Mg.However,the kinetic performance and cyclic stability of cathode materials a...Magnesium-ion batteries(MIBs)have promising applications because of their high theoretical capacity and the natural abundance of magnesium Mg.However,the kinetic performance and cyclic stability of cathode materials are limited by the strong interactions between Mg ions and the crystal lattice.Here,we demonstrate the unique Mg^(2+)-ion storage mechanism of a hierarchical accordion-like vanadium oxide/carbon heterointerface(V_(2)O_(3)@C),where the V_(2)O_(3) crystalline structure is reconstructed into a MgV_(3)O_(7)·H_(2)O phase through an anodic hydration reaction upon first cycle,for the improved kinetic and cyclic performances.As verified by in situ/ex situ spectroscopic and electrochemical analyses,the fast charge transfer kinetics of the V_(2)O_(3)@C cathode were due to the crystal-reconstruction and chemically coupled heterointerface.The V_(2)O_(3)@C demonstrated an ultrahigh rate capacity of 130.4 mAh g^(-1)at 50000 mA g^(-1)and 1000 cycles,achieving a Coulombic efficiency of 99.6%.The high capacity of 381.0 mA h g^(-1)can be attributed to the reversible Mg^(2+)-ion intercalation mechanism observed in the MgV_(3)O_(7)·H_(2)O phase using a 0.3 M Mg(TFSI)2/ACN(H_(2)O)electrolyte.Additionally,within the voltage range of 2.25 V versus Mg/Mg^(2+),the V_(2)O_(3)@C exhibited a capacity of 245.1 mAh g^(-1)when evaluated with magnesium metal in a 0.3 M Mg(TFSI)^(2+)0.25 M MgCl_(2)/DME electrolyte.These research findings have important implications for understanding the relationship between the Mg-ion storage mechanism and reconstructed crystal phase of vanadium oxides as well as the heterointerface reconstruction for the rational design of MIB cathode materials.展开更多
With the increasing prevalence of lithium-ion batteries(LIBs)applications,the demand for high-capacity next-generation materials has also increased.SiO_(x)is currently considered a promising anode material due to its ...With the increasing prevalence of lithium-ion batteries(LIBs)applications,the demand for high-capacity next-generation materials has also increased.SiO_(x)is currently considered a promising anode material due to its exceptionally high capacity for LIBs.However,the significant volumetric changes of SiO_(x)during cycling and its initial Coulombic efficiency(ICE)complicate its use,whether alone or in combination with graphite materials.In this study,a three-dimensional conductive binder network with high electronic conductivity and robust elasticity for graphite/SiO_(x)blended anodes was proposed by chemically anchoring carbon nanotubes and carboxymethyl cellulose binders using tannic acid as a chemical cross-linker.In addition,a dehydrogenation-based prelithiation strategy employing lithium hydride was utilized to enhance the ICE of SiO_(x).The combination of these two strategies increased the CE of SiO_(x)from 74%to87%and effectively mitigated its volume expansion in the graphite/SiO_(x)blended electrode,resulting in an efficient electron-conductive binder network.This led to a remarkable capacity retention of 94%after30 cycles,even under challenging conditions,with a high capacity of 550 mA h g^(-1)and a current density of 4 mA cm^(-2).Furthermore,to validate the feasibility of utilizing prelithiated SiO_(x)anode materials and the conductive binder network in LIBs,a full cell incorporating these materials and a single-crystalline Ni-rich cathode was used.This cell demonstrated a~27.3%increase in discharge capacity of the first cycle(~185.7 mA h g^(-1))and exhibited a cycling stability of 300 cycles.Thus,this study reports a simple,feasible,and insightful method for designing high-performance LIB electrodes.展开更多
P-i-n type perovskite solar cells(PSCs)manifest some promising advantages in terms of remarkable operational stability,low-temperature processability,and compatibility for multi-junction devices,whereas they have rela...P-i-n type perovskite solar cells(PSCs)manifest some promising advantages in terms of remarkable operational stability,low-temperature processability,and compatibility for multi-junction devices,whereas they have relatively low efficiency compared to n-i-p type PSCs because of mismatched energy level alignment and poor interface quality at both n-and p-type contacts.Recently,great progress has been achieved in the p-i-n type PSCs,and efficiencies exceeding 25%have been reported from different research groups.Herein,state-of-the-art strategies in the deployment of high-performance p-i-n type PSCs have been systematically reviewed including engineering top-surface and buried interface of perovskitefilms with eliminated non-radiative charge recombination,modulating conduction types of the perovskites with well aligned energy level to facilitate charge transport,and designing effective hole transport materials for lossless charge extraction,and so on,based on which perspectives in the further design of efficient,stable and scalable p-i-n type PSCs are provided from the aspects of materials design,device fabrication,scalability and functionalization.展开更多
Despite the safety,low cost,and high theoretical capacity(820 mA h g^(-1))of Zn metal anodes,the practical application of aqueous Zn metal batteries remains a critical challenge due to the Zn dendrite growth,corrosion...Despite the safety,low cost,and high theoretical capacity(820 mA h g^(-1))of Zn metal anodes,the practical application of aqueous Zn metal batteries remains a critical challenge due to the Zn dendrite growth,corrosion,and hydrogen evolution reaction.Herein,we demonstrate the MXene ink hosting Zn metal anodes(MX@Zn)for high-performance and patternable Zn metal full batteries.The as-designed MX@Zn electrode is more facile and reversible than bare Zn and CC@Zn,as verified by better cyclic stability and lower overpotentials of symmetric cells with the plating capacity of 0.05 mA h cm^(-2)at 0.1 m A cm^(-2)and of 1 m A h cm^(-2)at 1 m A cm^(-2).The MX@Zn|MnO_(2)full cells deliver a high specific capacity of 281.9 m A h g^(-1),91.5%of the theoretical capacity,achieving 50%capacity retention from 60 mA g^(-1)to 300 mA g^(-1)and 79.7%of initial capacity after 200 cycles.Moreover,the patterned devices based on the MX@Zn electrode achieve high energy and power densities of 348.57 Wh kg^(-1)and 1556 W kg^(-1),respectively,along with a capacity retention of 64%and Coulombic efficiency of 99%over 500 cycles.The high performance of MX@Zn is attributed to the high electrical conductivity and hydrophilicity of MXene and rapid ion diffusion through the 3D interconnected porous channels.展开更多
文摘With the increasing spotlight in electric vehicles,there is a growing demand for high-energy-density batteries to enhance driving range.Consequently,several studies have been conducted on high-energy-density LiNi_(x)Co_(y)Mn_(z)O_(2)cathodes.However,there is a limit to permanent performance deterioration because of side reactions caused by moisture in the atmosphere and continuous microcracks during cycling as the Ni content to express high energy increases and the content of Mn and Co that maintain structural and electrochemical stabilization decreases.The direct modification of the surface and bulk regions aims to enhance the capacity and long-term performance of high-Ni cathode materials.Therefore,an efficient modification requires a study based on a thorough understanding of the degradation mechanisms in the surface and bulk region.In this review,a comprehensive analysis of various modifications,including doping,coating,concentration gradient,and single crystals,is conducted to solve degradation issues along with an analysis of the overall degradation mechanism occurring in high-Ni cathode materials.It also summarizes recent research developments related to the following modifications,aims to provide notable points and directions for post-studies,and provides valuable references for the commercialization of stable high-energy-density cathode materials.
基金supported by National R&D Program through the NRF funded by Ministry of Science and ICT(2021M3D1A2049315)and the Technology Innovation Program(20021909,Development of H2 gas detection films(?0.1%)and process technologies)funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea)supported by the Basic Science Program through the NRF of Korea,funded by the Ministry of Science and ICT,Korea.(Project Number:NRF-2022R1C1C1008845)supported by Basic Science Research Program through the NRF funded by the Ministry of Education(Project Number:NRF-2022R1A6A3A13073158)。
文摘Recent advances in functionally graded additive manufacturing(FGAM)technology have enabled the seamless hybridization of multiple functionalities in a single structure.Soft robotics can become one of the largest beneficiaries of these advances,through the design of a facile four-dimensional(4D)FGAM process that can grant an intelligent stimuli-responsive mechanical functionality to the printed objects.Herein,we present a simple binder jetting approach for the 4D printing of functionally graded porous multi-materials(FGMM)by introducing rationally designed graded multiphase feeder beds.Compositionally graded cross-linking agents gradually form stable porous network structures within aqueous polymer particles,enabling programmable hygroscopic deformation without complex mechanical designs.Furthermore,a systematic bed design incorporating additional functional agents enables a multi-stimuli-responsive and untethered soft robot with stark stimulus selectivity.The biodegradability of the proposed 4D-printed soft robot further ensures the sustainability of our approach,with immediate degradation rates of 96.6%within 72 h.The proposed 4D printing concept for FGMMs can create new opportunities for intelligent and sustainable additive manufacturing in soft robotics.
基金Korea Institute of Materials Science,Grant/Award Number:PNK9370National Research Foundation of Korea,Grant/Award Numbers:NRF-2021R1A2C1014280,NRF-2022R1C1C1011058,NRF-2022M3H446401037201Korea Institute of Science and Technology,Grant/Award Number:2E32581-23-092。
文摘Layered-type transition metal(TM)oxides are considered as one of the most promising cathodes for K-ion batteries because of the large theoretical gravimetric capacity by low molar mass.However,they suffer from severe structural change by de/intercalation and diffusion of K^(+)ions with large ionic size,which results in not only much lower reversible capacity than the theoretical capacity but also poor power capability.Thus,it is important to enhance the structural stability of the layered-type TM oxides for outstanding electrochemical behaviors under the K-ion battery system.Herein,it is investigated that the substitution of the appropriate Ti^(4+)contents enables a highly enlarged reversible capacity of P3-type KxCrO_(2) using combined studies of first-principles calculation and various experiments.Whereas the pristine P3-type KxCrO_(2) just exhibits the reversible capacity of∼120 mAh g^(−1) in the voltage range of 1.5-4.0 V(vs.K^(+)/K),the∼0.61 mol K^(+)corresponding to∼150 mAh g^(−1) can be reversible de/intercalated at the structure of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) under the same conditions.Furthermore,even at the high current density of 788 mA g^(−1),the specific capacity of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) is∼120 mAh g^(−1),which is∼81 times larger than that of the pristine P3-type KxCrO_(2).It is believed that this research can provide an effective strategy to improve the electrochemical performances of the cathode materials suffered by severe structural change that occurred during charge/discharge under not only K-ion battery system but also other rechargeable battery systems.
基金supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(2020R1I1A3054824)supported by the Basic Research Program through the NRF funded by the MSIT(Ministry of Science and ICT,2021R1A4A1032762)+2 种基金financial support by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)the Ministry of Trade,Industry&Energy(MOTIE)of the Republic of Korea(no.20213030010400)the financial support by the NRF grant funded by the MSIT under the contract numbers 2022R1C1C1011975。
文摘In recent years,metal halide perovskites have received significant attention as materials for next-generation optoelectronic devices owing to their excellent optoelectronic properties.The unprecedented rapid evolution in the device performance has been achieved by gaining an advanced understanding of the composition,crystal growth,and defect engineering of perovskites.As device performances approach their theoretical limits,effective optical management becomes essential for achieving higher efficiency.In this review,we discuss the status and perspectives of nano to micron-scale patterning methods for the optical management of perovskite optoelectronic devices.We initially discuss the importance of effective light harvesting and light outcoupling via optical management.Subsequently,the recent progress in various patterning/texturing techniques applied to perovskite optoelectronic devices is summarized by categorizing them into top-down and bottom-up methods.Finally,we discuss the perspectives of advanced patterning/texturing technologies for the development and commercialization of perovskite optoelectronic devices.
基金Ministry of Trade,Industry and Energy,Grant/Award Number:20010095Korea Evaluation Institute of Industrial Technology,Grant/Award Number:20012341。
文摘Lithium-sulfur batteries(LSBs)have drawn significant attention owing to their high theoretical discharge capacity and energy density.However,the dissolution of long-chain polysulfides into the electrolyte during the charge and discharge process(“shuttle effect”)results in fast capacity fading and inferior electrochemical performance.In this study,Mn_(2)O_(3)with an ordered mesoporous structure(OM-Mn_(2)O_(3))was designed as a cathode host for LSBs via KIT-6 hard templating,to effectively inhibit the polysulfide shuttle effect.OM-Mn_(2)O_(3)offers numerous pores to confine sulfur and tightly anchor the dissolved polysulfides through the combined effects of strong polar-polar interactions,polysulfides,and sulfur chain catenation.The OM-Mn_(2)O_(3)/S composite electrode delivered a discharge capacity of 561 mAh g^(-1) after 250 cycles at 0.5 C owing to the excellent performance of OM-Mn_(2)O_(3).Furthermore,it retained a discharge capacity of 628mA h g^(-1) even at a rate of 2 C,which was significantly higher than that of a pristine sulfur electrode(206mA h g^(-1)).These findings provide a prospective strategy for designing cathode materials for high-performance LSBs.
基金supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (2021R1A2C1014280)supported by the “Regional Innovation Strategy (RIS)” through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (MOE) (2021RIS-004)+1 种基金the Fundamental Research Program of the Korea Institute of Material Science (KIMS) (PNK9370)the calculation resources were supported by the Supercomputing Center in Korea Institute of Science and Technology Information (KISTI) (KSC-2022-CRE-0030)。
文摘The anionic redox has been widely studied in layered-oxide-cathodes in attempts to achieve highenergy-density for Na-ion batteries(NIBs).It is known that an oxidation state of Mn^(4+) or Ru^(5+) is essential for the anionic reaction of O^(2-)/O~-to occur during Na^(+) de/intercalation.However,here,we report that the anionic redox can occur in Ru-based layered-oxide-cathodes before full oxidation of Ru^(4+)/Ru^(5+).Combining studies using first-principles calculation and experimental techniques reveals that further Na^(+) deintercalation from P2-Na_(0.33)[Mg_(0.33)Ru_(0.67)]O_(2) is based on anionic oxidation after 0.33 mol Na^(+) deintercalation from P2-Na_(0.67)[Mg_(0.33)Ru_(0.67)]O_(2) with cationic oxidation of Ru^(4+)/Ru^(4.5+).Especially,it is revealed that the only oxygen neighboring 2Mg/1 Ru can participate in the anionic redox during Na^(+) de/intercalation,which implies that the Na-O-Mg arrangement in the P2-Na_(0.33)[M9_(0.33)Ru_(0.67)]O_(2) structure can dramatically lower the thermodynamic stability of the anionic redox than that of cationic redox.Through the O anionic and Ru cationic reaction,P2-Na_(0.67)[Mg_(0.33)Ru_(0.67)]O_(2) exhibits not only a large specific capacity of~172 mA h g^(-1) but also excellent power-capability via facile Na^(+) diffusion and reversible structural change during charge/discharge.These findings suggest a novel strategy that can increase the activity of anionic redox by modulating the local environment around oxygen to develop high-energy-density cathode materials for NIBs.
基金supported by the National Research Foundation of Korea (NRF)grant funded by the Korean government (MSIT) (NRF-2022R1C1C1011058)supported by the Korea Institute for Advancement of Technology (KIAT)grant funded by the Korean Government (MOTIE) (P0012748,HRD Program for Industrial Innovation).
文摘Batteries that utilize low-cost elemental sulfur and light metallic lithium as electrodes have great potential in achieving high energy density.However,building a lithium-sulfur(Li-S)full battery by controlling the electrolyte volume generally produces low practical energy because of the limited electrochemical Li-S redox.Herein,the high energy/high performance of a Li-S full battery with practical sulfur loading and minimum electrolyte volume is reported.A unique hybrid architecture configured with Ni-Co metal alloy(NiCo)and metal oxide(NiCoO_(2))nanoparticles heterogeneously anchored in carbon nanotube-embedded selfstanding carbon matrix is fabricated as a host for sulfur.This work demonstrates the considerable improvement that the hybrid structure's high conductivity and satisfactory porosity promote the transport of electrons and lithium ions in Li-S batteries.Through experimental and theoretical validations,the function of NiCo and NiCoO_(2) nanoparticles as an efficient polysulfide mediator is established.These particles afford polysulfide anchoring and catalytic sites for Li-S redox reaction,thus improving the redox conversion reversibility.Even at high sulfur loading,the nanostructured Ni-Co metal alloy and metal oxide enable to have stable cycling performance under lean electrolyte conditions both in half-cell and full-cell batteries using a graphite anode.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.-RS-2024-00335976)。
文摘Electrochemical nitrate reduction(ENR)is an economical and eco-friendly method for converting industrial wastewater into valuable ammonia under atmospheric conditions.The main challenge lies in designing and developing highly durable ENR electrocatalysts.This study introduces defect-rich mesoporous CuO_(x) nanowires electrocatalyst synthesized using a novel solution-flame(sol-flame)hybrid method to control mesoporosity and introduce surface defects,thereby enhancing the electrochemical nitrate-toammonia production performance.We found surface defects(oxygen vacancies and Cu^(+))and unique mesoporous nanowire structure composed of tightly interconnected nanoparticles.The sol-flamesynthesized CuO_(x) nanowires(sf-CuO NWs)achieved superior ammonia yield rate(0.51 mmol h^(-1)cm^(-2)),faradaic efficiency(97.3%),and selectivity(86.2%)in 1 M KOH electrolyte(2000 ppm nitrate).This performance surpasses that of non-porous and less-defective CuO NWs and is attributed to the increased surface area and rapid electron transport facilitated by the distinctive morphology and generated defects.Theoretical calculation further suggests oxygen vacancies enhance NO_(3)^(-)adsorption on the sf-CuO NWs’surface and mitigate the competing hydrogen evolution reaction.This study outlines a strategic design and simple synthesis approach for nanowire electrocatalysts that boost the efficiency of electrochemical nitrate-to-ammonia conversion.
基金National Research Foundation,Grant/Award Number:NRF-2020R1A3B2079803Korea Institute for Advancement of Technology,Grant/Award Number:P0026069。
文摘The polymeric gel electrolytes are attractive owing to their higher ionic conductivities than those of dry polymer electrolytes and lowered water activity for enlarged potential window.However,the ionic conductivity and mechanical strength of the Na-ion conducting polymeric gel electrolytes are limited by below 20 mS cm−1 and 2.2 MPa.Herein,we demonstrate Na-ion conducting and flexible polymeric hydrogel electrolytes of the chemically coupled poly(diallyldimethylammonium chloride)-dextrin-N,N′-methylene-bisacrylamide film immersed in NaClO_(4) solution(ex-DDA-Dex+NaClO_(4))for flexible sodium-ion hybrid capacitors(f-NIHC).In particular,the anion exchange reaction and synergistic interaction of ex-DDA-Dex with the optimum ClO_(4)−enable to greatly improve the ionic conductivity up to 27.63 mS cm−1 at 25◦C and electrochemical stability window up to 2.6 V,whereas the double networking structure leads to achieve both the mechanical strength(7.48 MPa)and softness of hydrogel electrolytes.Therefore,the f-NIHCs with the ex-DDA-Dex+NaClO_(4) achieved high specific and high-rate capacities of 192.04 F g^(−1)at 500 mA g^(−1)and 116.06 F g^(−1)at 10000 mA g^(−1),respectively,delivering a large energy density of 120.03Wh kg^(−1)at 906Wkg^(−1)and long cyclability of 70%over 500 cycles as well as demonstrating functional operation under mechanical stresses.
基金supported by National Natural Science Foundation of China(No.22178068)the Brain Pool(BP)program(No.2021H1D3A2A02045576)funded by National Research Foundation of KoreaNational Research Foundation of Korea grant funded by the Korea government(MSIT)(No.NRF-2020R1A3B2079803 and No.2021M3D1A2043791)。
文摘Si is considered as the promising anode materials for lithium-ion batteries(LIBs)owing to their high capacities of 4200 mAh g-1and natural abundancy.However,severe electrode pulverization and poor electronic and Li-ionic conductivities hinder their practical applications.To resolve the afore-mentioned problems,we first demonstrate a cation-mixed disordered lattice and unique Li storage mechanism of single-phase ternary GaSiP_(2)compound,where the liquid metallic Ga and highly reactive P are incorporated into Si through a ball milling method.As confirmed by experimental and theoretical analyses,the introduced Ga and P enables to achieve the stronger resistance against volume variation and metallic conductivity,respectively,while the cation-mixed lattice provides the faster Li-ionic diffusion capability than those of the parent GaP and Si phases.The resulting GaSiP_(2)electrodes delivered the high specific capacity of 1615 mAh g-1and high initial Coulombic efficiency of 91%,while the graphite-modified GaSiP_(2)(GaSiP_(2)@C)achieved 83%of capacity retention after 900 cycles and high-rate capacity of 800 at 10,000 mA g-1.Furthermore,the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)//Ga SiP_(2)@C full cells achieved the high specific capacity of 1049 mAh g-1after 100 cycles,paving a way for the rational design of high-performance LIB anode materials.
基金supported by the National Research Foundation of Korea (NRF) Grant funded by the Korean government (MSIT)(Nos. 2022R1A2C3012372 and 2022R1A4A1031182)Korea Institute for Advancement of Technology(KIAT)Competency Development Program for Industry Specialists of Korean Ministry of Trade,Industry and Energy Grant funded by the Korea Government(MOTIE)(No. P0008458, The Competency Development Program for Industry Specialist and No. P0017120, HRD program for Foster R&D specialist of parts for ecofriendly vehicle (xEV))
文摘Sluggish oxygen reduction reaction(ORR)kinetics are a major obstacle to developing intermediate-temperature solid-oxide fuel cells(IT-SOFCs).In particular,engineering the anion defect concentration at an interface between the cathode and electrolyte is important for facilitating ORR kinetics and hence improving the electrochemical performance.We developed the yttria-stabilized zirconia(YSZ)nanofiber(NF)-based composite cathode,where the oxygen vacancy concentration is controlled by varying the dopant cation(Y2O3)ratio in the YSZ NFs.The composite cathode with the optimized oxygen vacancy concentration exhibits maximum power densities of 2.66 and 1.51 W cm^(−2)at 700 and 600℃,respectively,with excellent thermal stability at 700℃ over 500 h under 1.0 A cm^(−2).Electrochemical impedance spectroscopy and distribution of relaxation time analysis revealed that the high oxygen vacancy concentration in the NF-based scaffold facilitates the charge transfer and incorporation reaction occurred at the interfaces between the cathode and electrolyte.Our results demonstrate the high feasibility and potential of interface engineering for achieving IT-SOFCs with higher performance and stability.
基金supported by the National Research Foundation of Korea grant funded by the Korea government (NRF2021R1A2C1014280)the Fundamental Research Program of the Korea Institute of Material Science (PNK9370)。
文摘Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions during anionic redox reactions lead to poor electrochemical performance with sluggish kinetics.Here, we propose a synergy of Li-Cu cations in harnessing the full potential of oxygen redox, through Li displacement and suppressed phase transition in P3-type layered oxide cathode. P3-type Na_(0.7)[Li_(0.1)Cu_(0.2)Mn_(0.7)]O_(2) cathode delivers a large specific capacity of ~212 mA h g^(-1)at 15 mA g^(-1). The discharge capacity is maintained up to ~90% of the initial capacity after 100 cycles, with stable occurrence of the oxygen redox in the high-voltage region. Through advanced experimental analyses and first-principles calculations, it is confirmed that a stepwise redox reaction based on Cu and O ions occurs for the charge-compensation mechanism upon charging. Based on a concrete understanding of the reaction mechanism, the Li displacement by the synergy of Li-Cu cations plays a crucial role in suppressing the structural change of the P3-type layered material under the oxygen redox reaction, and it is expected to be an effective strategy for stabilizing the oxygen redox in the layered oxides of Na-ion batteries.
基金National Research Foundation of Korea,Grant/Award Numbers:2022M3J1A1085410,RS-2023-00208983。
文摘Lithium-oxygen(Li-O_(2))batteries are an emerging energy storage alternative with the potential to meet the recent increase in demand for high-energy-density batteries.From a practical viewpoint,lithium-air(Li-Air)batteries using ambient air instead of pure oxygen could be the final goal.However,the slow oxygen reduction and evolution reactions interfere with reversible cell operation during cycling.Therefore,research continues to explore various catalyst materials.The present study attempts to improve the performance of Li-Air batteries by using porphyrin-based materials known to have catalytic effects in Li-O_(2) batteries.The results confirm that the iron phthalocyanine(FePc)catalyst not only exhibits a catalytic effect in an air atmosphere with a low oxygen fraction but also suppresses electrolyte decomposition by stabilizing superoxide radical ions(O_(2)^(−))at a high voltage range.Density functional theory calculations are used to gain insight into the exact FePc-mediated catalytic mechanism in Li-Air batteries,and various ex situ and in situ analyses reveal the reversible reactions and structural changes in FePc during electrochemical reaction.This study provides a practical solution to ultimately realize an air-breathing battery using nature-friendly catalyst materials.
基金supported by the Ministry of Science and ICT(MSIT)of the Republic of Korea(00302646)supported by the National Research Foundation of Korea grant funded by the Korean Government(MSIT)(NRF-2022R1A4A1019296,1345374646,2022M3J1A1064315).
文摘Perovskite solar cells(PSCs)have developed rapidly,positioning them as potential candidates for nextgeneration renewable energy sources.However,conventional trial-and-error approaches and the vast compositional parameter space continue to pose challenges in the pursuit of exceptional performance and high stability of perovskite-based optoelectronics.The increasing demand for novel materials in optoelectronic devices and establishment of substantial databases has enabled data-driven machinelearning(ML)approaches to swiftly advance in the materials field.This review succinctly outlines the fundamental ML procedures,techniques,and recent breakthroughs,particularly in predicting the physical characteristics of perovskite materials.Moreover,it highlights research endeavors aimed at optimizing and screening materials to enhance the efficiency and stability of PSCs.Additionally,this review highlights recent efforts in using characterization data for ML,exploring their correlations with material properties and device performance,which are actively being researched,but they have yet to receive significant attention.Lastly,we provide future perspectives,such as leveraging Large Language Models(LLMs)and text-mining,to expedite the discovery of novel perovskite materials and expand their utilization across various optoelectronic fields.
基金supported by SKKU Excellence in Research Award Research Fund,Sungkyunkwan University,2023.
文摘Perovskite solar cells(PSCs)have shown remarkable advancements and achieved impressive power conversion efficiencies since their initial introduction in 2012.However,challenges regarding stability,quality,and sustainability must be addressed for their successful commercial use.This review analyses the recent studies and challenges related to the operating life and end-of-life utilization of PSCs.Strategies to enhance the stability and mitigate the toxic Pb leakage in operational and recycling approaches of discarded PSCs post their end-of-life are examined to establish a viable and sustainable PSC industry.Additionally,future research directions are proposed for the advancements in the PSC industry.The goal is to ensure high efficiency as well as economic and environmental sustainability throughout the lifecycle of PSCs.
基金supported by the National Research Foundation of Korea grant funded by the Korea government(MSIT)(NRF-2020R1A3B2079803)the computational time provided by KISTI(KSC-2023-CRE-0166).
文摘Dual ion storage hybrid supercapacitors(HsCs)are considered as a promising device to overcome the limited energy density of existing supercapacitors while preserving high power and long cyclability.However,the development of high-capacity anion-storing materials,which can be paired with fast charg-ing capacitive electrodes,lags behind cation-storing counterparts.Herein,we demonstrate the surface faradaic OH-storage mechanism of anion storing perovskite oxide composites and their application in high-performance dual ion HsCs.The oxygen vacancy and nanoparticle size of the reduced LaMnO_(3)(r-LaMnO_(3))were controlled,while r-LaMnO_(3) was chemically coupled with ozonated carbon nanotubes(oCNTs)for the improved anion storing capacity and cycle performance.As taken by in-situ and ex-situ spectroscopic and computational analyses,OH-ions are inserted into the oxygen vacancies coordi-nating with octahedral Mn with the increase in the oxidation state of Mn during the charging process or vice versa.Configuring OH-storing r-LaMnO_(3)/oCNT composite with Na*storing MXene,the as-fabricated aqueous dual ion HSCs achieved the cycle performance of 73.3%over 10,000 cycles,delivering the max-imum energy and power densities of 47.5 w h kg^(-1) and 8 kw kg^(-1),respectively,far exceeding those of previously reported aqueous anion and dual ion storage cells.This research establishes a foundation for the unique anion storage mechanism of the defect engineered perovskite oxides and the advancement of dual ion hybrid energy storage devices with high energy and power densities.
基金National Research Foundation of Korea,Grant/Award Number:NRF2020R1A3B2079803。
文摘Magnesium-ion batteries(MIBs)have promising applications because of their high theoretical capacity and the natural abundance of magnesium Mg.However,the kinetic performance and cyclic stability of cathode materials are limited by the strong interactions between Mg ions and the crystal lattice.Here,we demonstrate the unique Mg^(2+)-ion storage mechanism of a hierarchical accordion-like vanadium oxide/carbon heterointerface(V_(2)O_(3)@C),where the V_(2)O_(3) crystalline structure is reconstructed into a MgV_(3)O_(7)·H_(2)O phase through an anodic hydration reaction upon first cycle,for the improved kinetic and cyclic performances.As verified by in situ/ex situ spectroscopic and electrochemical analyses,the fast charge transfer kinetics of the V_(2)O_(3)@C cathode were due to the crystal-reconstruction and chemically coupled heterointerface.The V_(2)O_(3)@C demonstrated an ultrahigh rate capacity of 130.4 mAh g^(-1)at 50000 mA g^(-1)and 1000 cycles,achieving a Coulombic efficiency of 99.6%.The high capacity of 381.0 mA h g^(-1)can be attributed to the reversible Mg^(2+)-ion intercalation mechanism observed in the MgV_(3)O_(7)·H_(2)O phase using a 0.3 M Mg(TFSI)2/ACN(H_(2)O)electrolyte.Additionally,within the voltage range of 2.25 V versus Mg/Mg^(2+),the V_(2)O_(3)@C exhibited a capacity of 245.1 mAh g^(-1)when evaluated with magnesium metal in a 0.3 M Mg(TFSI)^(2+)0.25 M MgCl_(2)/DME electrolyte.These research findings have important implications for understanding the relationship between the Mg-ion storage mechanism and reconstructed crystal phase of vanadium oxides as well as the heterointerface reconstruction for the rational design of MIB cathode materials.
基金supported by the National Research Foundation(NRF)of Korea grant funded by the Korean government(MSIT)(No.NRF-2021 M3 H4A1A02045962).
文摘With the increasing prevalence of lithium-ion batteries(LIBs)applications,the demand for high-capacity next-generation materials has also increased.SiO_(x)is currently considered a promising anode material due to its exceptionally high capacity for LIBs.However,the significant volumetric changes of SiO_(x)during cycling and its initial Coulombic efficiency(ICE)complicate its use,whether alone or in combination with graphite materials.In this study,a three-dimensional conductive binder network with high electronic conductivity and robust elasticity for graphite/SiO_(x)blended anodes was proposed by chemically anchoring carbon nanotubes and carboxymethyl cellulose binders using tannic acid as a chemical cross-linker.In addition,a dehydrogenation-based prelithiation strategy employing lithium hydride was utilized to enhance the ICE of SiO_(x).The combination of these two strategies increased the CE of SiO_(x)from 74%to87%and effectively mitigated its volume expansion in the graphite/SiO_(x)blended electrode,resulting in an efficient electron-conductive binder network.This led to a remarkable capacity retention of 94%after30 cycles,even under challenging conditions,with a high capacity of 550 mA h g^(-1)and a current density of 4 mA cm^(-2).Furthermore,to validate the feasibility of utilizing prelithiated SiO_(x)anode materials and the conductive binder network in LIBs,a full cell incorporating these materials and a single-crystalline Ni-rich cathode was used.This cell demonstrated a~27.3%increase in discharge capacity of the first cycle(~185.7 mA h g^(-1))and exhibited a cycling stability of 300 cycles.Thus,this study reports a simple,feasible,and insightful method for designing high-performance LIB electrodes.
基金supported by the National Research Foundation of Korea(NRF)grants funded by the Korean government(MSIT)under contract NRF-2021R1A3B1076723(Research Leader Program)and NRF2022M3J1A1085280(Carbon Neutral Technology Program)supported by the Korea Evaluation Institute of Industrial Technology under contract 20016588.
文摘P-i-n type perovskite solar cells(PSCs)manifest some promising advantages in terms of remarkable operational stability,low-temperature processability,and compatibility for multi-junction devices,whereas they have relatively low efficiency compared to n-i-p type PSCs because of mismatched energy level alignment and poor interface quality at both n-and p-type contacts.Recently,great progress has been achieved in the p-i-n type PSCs,and efficiencies exceeding 25%have been reported from different research groups.Herein,state-of-the-art strategies in the deployment of high-performance p-i-n type PSCs have been systematically reviewed including engineering top-surface and buried interface of perovskitefilms with eliminated non-radiative charge recombination,modulating conduction types of the perovskites with well aligned energy level to facilitate charge transport,and designing effective hole transport materials for lossless charge extraction,and so on,based on which perspectives in the further design of efficient,stable and scalable p-i-n type PSCs are provided from the aspects of materials design,device fabrication,scalability and functionalization.
基金supported by financial support from the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(NRF-2020R1A3B2079803 and NRF2019K1A3A1A21032033),Republic of Korea。
文摘Despite the safety,low cost,and high theoretical capacity(820 mA h g^(-1))of Zn metal anodes,the practical application of aqueous Zn metal batteries remains a critical challenge due to the Zn dendrite growth,corrosion,and hydrogen evolution reaction.Herein,we demonstrate the MXene ink hosting Zn metal anodes(MX@Zn)for high-performance and patternable Zn metal full batteries.The as-designed MX@Zn electrode is more facile and reversible than bare Zn and CC@Zn,as verified by better cyclic stability and lower overpotentials of symmetric cells with the plating capacity of 0.05 mA h cm^(-2)at 0.1 m A cm^(-2)and of 1 m A h cm^(-2)at 1 m A cm^(-2).The MX@Zn|MnO_(2)full cells deliver a high specific capacity of 281.9 m A h g^(-1),91.5%of the theoretical capacity,achieving 50%capacity retention from 60 mA g^(-1)to 300 mA g^(-1)and 79.7%of initial capacity after 200 cycles.Moreover,the patterned devices based on the MX@Zn electrode achieve high energy and power densities of 348.57 Wh kg^(-1)and 1556 W kg^(-1),respectively,along with a capacity retention of 64%and Coulombic efficiency of 99%over 500 cycles.The high performance of MX@Zn is attributed to the high electrical conductivity and hydrophilicity of MXene and rapid ion diffusion through the 3D interconnected porous channels.
