Knowing the optimal operating parameters of Stirling engines is important for efficient combustion through adaptability to changed pressures and oxygen atmospheres. In this study, the optimum operating conditions for ...Knowing the optimal operating parameters of Stirling engines is important for efficient combustion through adaptability to changed pressures and oxygen atmospheres. In this study, the optimum operating conditions for efficient combustion in a singular Stirling engine combustor at different oxygen atmospheres were investigated and determined. Numerical simulations were performed to investigate the effects of ejection ratio and pressure on combustion performance. In an oxygen/carbon dioxide atmosphere, the results show that increasing the ejection ratio substantially alters the flame distribution in the Stirling engine combustor, increasing heat transfer and external combustion efficiency. In contrast, increasing the ejection ratio reduces the average and maximum temperatures of the Stirling engine combustor. Increased pressure affects the flame distribution in the Stirling engine combustor and impedes the flow and convective heat transfer in the combustor, reducing the overall external combustion efficiency at pressures above 6.5 MPa. In an air/carbon dioxide atmosphere, an increased ejection ratio reduces the average and maximum temperatures in the Stirling engine combustor. However, the overall flame distribution does not change substantially. The external combustion efficiency tends to increase and then decrease because of two opposing factors: the increase in the convective heat transfer coefficient and the decrease in the temperature difference. Increasing pressure inhibits forced convection heat transfer in the Stirling engine combustor, reducing external combustion efficiency, which drops from 78% to 65% when pressure increases from 0.2 MPa to 0.5 MPa.展开更多
Point defect engineering endows catalysts with novel physical and chemical properties,elevating their electrocatalytic efficiency.The introduction of defects emerges as a promising strategy,effectively modifying the e...Point defect engineering endows catalysts with novel physical and chemical properties,elevating their electrocatalytic efficiency.The introduction of defects emerges as a promising strategy,effectively modifying the electronic structure of active sites.This optimization influences the adsorption energy of intermediates,thereby mitigating reaction energy barriers,altering paths,enhancing selectivity,and ultimately improving the catalytic efficiency of electrocatalysts.To elucidate the impact of defects on the electrocatalytic process,we comprehensively outline the roles of various point defects,their synthetic methodologies,and characterization techniques.Importantly,we consolidate insights into the relationship between point defects and catalytic activity for hydrogen/oxygen evolution and CO_(2)/O_(2)/N_(2) reduction reactions by integrating mechanisms from diverse reactions.This underscores the pivotal role of point defects in enhancing catalytic performance.At last,the principal challenges and prospects associated with point defects in current electrocatalysts are proposed,emphasizing their role in advancing the efficiency of electrochemical energy storage and conversion materials.展开更多
High temperature piezoelectric energy harvester(HTPEH)is an important solution to replace chemical battery to achieve independent power supply of HT wireless sensors.However,simultaneously excellent performances,inclu...High temperature piezoelectric energy harvester(HTPEH)is an important solution to replace chemical battery to achieve independent power supply of HT wireless sensors.However,simultaneously excellent performances,including high figure of merit(FOM),insulation resistivity(ρ)and depolarization temperature(Td)are indispensable but hard to achieve in lead-free piezoceramics,especially operating at 250°C has not been reported before.Herein,well-balanced performances are achieved in BiFeO3–BaTiO3 ceramics via innovative defect engineering with respect to delicate manganese doping.Due to the synergistic effect of enhancing electrostrictive coefficient by polarization configuration optimization,regulating iron ion oxidation state by high valence manganese ion and stabilizing domain orientation by defect dipole,comprehensive excellent electrical performances(Td=340°C,ρ250°C>10^(7)Ωcm and FOM_(250°C)=4905×10^(–15)m^(2)N^(−1))are realized at the solid solubility limit of manganese ions.The HT-PEHs assembled using the rationally designed piezoceramic can allow for fast charging of commercial electrolytic capacitor at 250°C with high energy conversion efficiency(η=11.43%).These characteristics demonstrate that defect engineering tailored BF-BT can satisfy high-end HT-PEHs requirements,paving a new way in developing selfpowered wireless sensors working in HT environments.展开更多
Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,th...Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.展开更多
Solution-processed Cu(In,Ga)Se_(2)(CIGS) solar cells suffer from serious carrier recombination and power conversion efficiency(PCE) loss because of the poor film properties and easy formation of defects.Herein, we pro...Solution-processed Cu(In,Ga)Se_(2)(CIGS) solar cells suffer from serious carrier recombination and power conversion efficiency(PCE) loss because of the poor film properties and easy formation of defects.Herein, we propose Ag&Se co-selenization strategy to enhance the crystallization and passivate harmful defects of the CIGS films. The formation of Ag-Se phase during the selenization process enables the formation of large grains and suppresses the deep level defects. It is found that Ag doping can enlarge the depletion region width, lower the Urbach energy and prolong the carrier lifetime. As a result, a champion solution-processed CIGS solar cell presents a high efficiency of 16.48% with the highly improved opencircuit voltage(VOC) of 662 m V and fill factor(FF) of 75.8%. This work provides an efficient strategy to prepare high quality solution-processed CIGS films for high-performance CIGS solar cells.展开更多
Stress accumulation is a key factor leading to sodium storage performance deterioration for NiSe_(2)-based anodes.Therefore,inhibiting the concentrated local stress during the sodiataion/desodiation process is crucial...Stress accumulation is a key factor leading to sodium storage performance deterioration for NiSe_(2)-based anodes.Therefore,inhibiting the concentrated local stress during the sodiataion/desodiation process is crucial for acquiring stable NiSe2-based materials for sodium-ion batteries(SIBs),Herein,a stress dissipation strategy driven by architecture engineering is proposed,which can achieve ultrafast and ultralong sodium storage properties.Different from the conventional sphere-like or rod-like architecture,the three-dimensional(3D)flower-like NiSe_(2)@C composite is delicately designed and assembled with onedimensional nanorods and carbon framework.More importantly,the fundamental mechanism of improved structure stability is unveiled by simulations and experimental results simultaneously.It demonstrates that this designed multidimensional flower-like architecture with dispersed nanorods can balance the structural mismatch,avoid concentrated local strain,and relax the internal stress,mainly induced by the unavoidable volume variation during the repeated conversion processes.Moreover,it can provide more Na^(+)-storage sites and multi-directional migration pathways,leading to a fast Na^(+)-migration channel with boosted reaction kinetic.As expected,it delivers superior rate performance(441 mA h g^(-1)at 5.0 A g^(-1))and long cycling stability(563 mA h g^(-1)at 1.0 A g^(-1)over 1000 cycles)for SIBs.This work provides useful insights for designing high-performance conversion-based anode materials for SIBs.展开更多
Finding ways to produce dense and smooth perovskite films with negligible defects is vital for achieving high-efficiency perovskite solar cells(PSCs).Herein,we aim to enhance the quality of the perovskite films throug...Finding ways to produce dense and smooth perovskite films with negligible defects is vital for achieving high-efficiency perovskite solar cells(PSCs).Herein,we aim to enhance the quality of the perovskite films through the utilization of a multifunctional additive in the perovskite anti-solvent,a strategy referred to as anti-solvent additive engineering.Specifically,we introduce ortho-substituted-4′-(4,4″-di-tertbutyl-1,1′:3′,1″-terphenyl)-graphdiyne(o-TB-GDY)as an AAE additive,characterized by its sp/sp^2-cohybridized and highlyπ-conjugated structure,into the anti-solvent.o-TB-GDY not only significantly passivates undercoordinated lead defects(through potent coordination originating from specific highπ–electron conjugation),but also serves as nucleation seeds to effectively enhance the nucleation and growth of perovskite crystals.This markedly reduces defects and non-radiative recombination,thereby increasing the power conversion efficiency(PCE)to 25.62%(certified as 25.01%).Meanwhile,the PSCs exhibit largely enhanced stability,maintaining 92.6%of their initial PCEs after 500 h continuous 1-sun illumination at~23°C in a nitrogen-filled glove box.展开更多
Practical Zn metal batteries have been hindered by several challenges,including Zn dendrite growth,undesirable side reactions,and unstable electrode/electrolyte interface.These issues are particularly more serious in ...Practical Zn metal batteries have been hindered by several challenges,including Zn dendrite growth,undesirable side reactions,and unstable electrode/electrolyte interface.These issues are particularly more serious in low-concentration electrolytes.Herein,we design a Zn salt-mediated electrolyte with in situ ring-opening polymerization of the small molecule organic solvent.The Zn(TFSI)_(2)salt catalyzes the ring-opening polymerization of(1,3-dioxolane(DOL)),generating oxidation-resistant and non-combustible long-chain polymer(poly(1,3-dioxolane)(pDOL)).The pDOL reduces the active H_(2)O molecules in electrolyte and assists in forming stable organic–inorganic gradient solid electrolyte interphase with rich organic constituents,ZnO and ZnF_(2).The introduction of pDOL endows the electrolyte with several advantages:excellent Zn dendrite inhibition,improved corrosion resistance,widened electrochemical window(2.6 V),and enhanced low-temperature performance(freezing point=-34.9°C).Zn plating/stripping in pDOL-enhanced electrolyte lasts for 4200 cycles at 99.02%Coulomb efficiency and maintains a lifetime of 8200 h.Moreover,Zn metal anodes deliver stable cycling for 2500 h with a high Zn utilization of 60%.A Zn//VO_(2)pouch cell assembled with lean electrolyte(electrolyte/capacity(E/C=41 mL(Ah)^(-1))also demonstrates a capacity retention ratio of 92%after 600 cycles.These results highlight the promising application prospects of practical Zn metal batteries enabled by the Zn(TFSI)2-mediated electrolyte engineering.展开更多
Formamidinium lead bromide(FAPbBr_(3))perovskite nanocrystals(NCs)are promising for display and lighting due to their ultra-pure green emission.However,the thermal quenching will exacerbate their performance degradati...Formamidinium lead bromide(FAPbBr_(3))perovskite nanocrystals(NCs)are promising for display and lighting due to their ultra-pure green emission.However,the thermal quenching will exacerbate their performance degradation in practical applications,which is a common issue for halide perovskites.Here,we reported the heat-resistant FAPbBr_(3)NCs prepared by a ligand-engineered room-temperature synthesis strategy.An aromatic amine,specificallyβ-phenylethylamine(PEA)or 3-fluorophenylethylamine(3-F-PEA),was incoporated as the short-chain ligand to expedite the crystallization rate and control the size distribution of FAPbBr_(3)NCs.Employing this ligand engineering approach,we synthesized high quality FAPbBr_(3)NCs with uniform grain size and reduced long-chain alkyl ligands,resulting in substantially suppressed thermal quenching and enhanced carrier transportation in the perovskite NCs films.Most notably,more than 90%of the room temperature PL intensity in the 3-F-PEA modified FAPbBr_(3)NCs film was preserved at 380 K.Consequently,we fabricated ultra-pure green EL devices with a room temperature external quantum efficiency(EQE)as high as 21.9%at the luminance of above 1,000 cd m^(-2),and demonstrated less than 10%loss in EQE at 343 K.This study introduces a novel room temperature method to synthesize efficient FAPbBr_(3)NCs with exceptional thermal stability,paving the way for advanced optoelectronic device applications.展开更多
Flexible perovskite solar cells(fPSCs)have demonstrated commercial viability because of their promising lightness,flexibility,and low-cost advantages.However,in most applications,the fPSCs suffer from constant externa...Flexible perovskite solar cells(fPSCs)have demonstrated commercial viability because of their promising lightness,flexibility,and low-cost advantages.However,in most applications,the fPSCs suffer from constant external stress,such as being kept at a convex bending state,imposing external stress on the brittle perovskite films and causing the fPSCs long-term stability problems.Overcoming these issues is vital.Herein,we propose an effective way to enhance the stability of the fPSCs under convex bending by modulating the residual stress of perovskite film for the first time.Specifically,we have carefully designed a synergistic strain engineering to toughen the perovskite films by introducing 1-butyl-3-methylimidazolium tetrafluoroborate,citric acid,and a novel cross-linker,5-(1,2-dithiolan-3-yl)pentanoate into perovskite films simultaneously.Besides passivating the perovskite films,the multiple additives effectively convert the residual stress within the perovskite films from tensile to compressive type to alleviate the detrimental impact of bending on the flexible perovskite films.As a result,the optimal efficiencies of triple-additive modified fPSCs have achieved 22.19%(0.06 cm^(2))and 19.44%(1.02 cm^(2)).More importantly,the strategy could significantly improve the stability of the perovskite films and fPSCs at a convex bending state.Our approach is inductive for the future practical field applications of high-performance fPSCs.展开更多
The ability to replicate the microenvironment of the human body through the fabrication of scaffolds is a significant achievement in the biomedical field.However,the search for the ideal scaffold is still in its infan...The ability to replicate the microenvironment of the human body through the fabrication of scaffolds is a significant achievement in the biomedical field.However,the search for the ideal scaffold is still in its infancy and there are significant challenges to overcome.In the modern era,the scientific community is increasingly turned to natural substances due to their superior biological ability,lower cost,biodegradability,and lower toxicity than synthetic lab-made products.Chitosan is a well-known polysaccharide that has recently garnered a high amount of attention for its biological activities,especially in 3D bone tissue engineering.Chitosan closely matches the native tissues and thus stands out as a popular candidate for bioprinting.This review focuses on the potential of chitosan-based scaffolds for advancements and the drawbacks in bone treatment.Chitosan-based nanocomposites have exhibited strong mechanical strength,water-trapping ability,cellular interaction,and biodegradability.Chitosan derivatives have also encouraged and provided different routes for treatment and enhanced biological activities.3D tailored bioprinting has opened new doors for designing and manufacturing scaffolds with biological,mechanical,and topographical properties.展开更多
Three large π-conjugated and imine-based COFs,named TFP-TAB,TFP-TTA,and TTA-TTB,were synthesized via the ordered incorporation of benzene and triazine rings in the same host framework to study how the structural unit...Three large π-conjugated and imine-based COFs,named TFP-TAB,TFP-TTA,and TTA-TTB,were synthesized via the ordered incorporation of benzene and triazine rings in the same host framework to study how the structural units affect the efficiency of CO_(2)photoreduction.Results from both experiments and density-functional theory(DFT)calculations indicate the separation and transfer of the photoinduced charges is highly related to the triazine-N content and the conjugation degree in the skeletons of COFs.High-efficiency CO_(2)photoreduction can be achieved by rationally adjusting the number and position of both benzene and triazine rings in the COFs.Specifically,TTA-TTB,with orderly interlaced triazine-benzene heterojunctions,can suppress the recombination probability of electrons and holes,which effectively immobilizes the key species(COOH)and lowers the free energy change of the potential-determining step,and thus exhibits a superior visible-light-induced photocatalytic activity that yields 121.7 μmol HCOOH g^(-1)h^(-1).This research,therefore,helps to elucidate the effects of the different structural blocks in COFs on inherent heterogeneous photocatalysis for CO_(2)reduction at a molecular level.展开更多
Lithium-rich manganese-based cathodes(LRMs)have garnered significant attention as promising candidates for highenergy-density batteries due to their exceptional specific capacity exceeding 300 mAh/g,achieved through s...Lithium-rich manganese-based cathodes(LRMs)have garnered significant attention as promising candidates for highenergy-density batteries due to their exceptional specific capacity exceeding 300 mAh/g,achieved through synergistic anionic and cationic redox reactions.However,these materials face challenges including oxygen release-induced structural degradation and consequent capacity fading.To address these issues,strategies such as surface modification and bulk phase engineering have been explored.In this study,we developed a facile and cost-effective quenching approach that simultaneously modifies both surface and bulk characteristics.Multi-scale characterization and computational analysis reveal that rapid cooling partially preserves the high-temperature disordered phase in the bulk structure,thereby enhancing the structural stability.Concurrently,Li^(+)/H^(+)exchange at the surface forms a robust rock-salt/spinel passivation layer,effectively suppressing oxygen evolution and mitigating interfacial side reactions.This dual modification strategy demonstrates a synergistic stabilization effect.The enhanced oxygen redox activity coexists with the improved structural integrity,leading to superior electrochemical performance.The optimized cathode delivers an initial discharge capacity approaching 307.14 mAh/g at 0.1 C and remarkable cycling stability with 94.12%capacity retention after 200 cycles at 1 C.This study presents a straightforward and economical strategy for concurrent surface–bulk modification,offering valuable insights for designing high-capacity LRM cathodes with extended cycle life.展开更多
One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible p...One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible phases.Nevertheless,the regulation of intermolecular interactions between plasticizers and rigid and flexible phases has been largely overlooked.Here,an intermolecular interaction engineering strategy is carried out with well-chosen dual-plasticize within qua si-sol id-state polymer electrolytes(QSPEs).Succinonitrile exhibits a stronger affinity towards rigid phase hydrogenated nitrile butadiene rubber(HNBR),while propene carbonate demonstrates a stronger affinity towards flexible segments poly(propylene carbonate)(PPC).This tailored intermolecular interaction engineering allows for differential plasticization of the polymer's rigid and flexible phases,thereby achieving a balance between ionic conductivity and mechanical strength.The QSPE have both higher ionic conductivity(1.04×10^(-4)S cm^(-1)at 30℃),t_(Li+)(0.55),and tensile strength(0.76 MPa).Li//Li symmetric cells maintaining performance over1100 h at 0.1 mA cm^(-2)and Li//LiFePO_(4)cells retaining 85.0%capacity after 700 cycles at 1.0 C.It is a unique angle to employ intermolecular interaction engineering in QSPEs through dual-plasticizer approach combined with CO_(2)-based polymer materials.This sustainable strategy combining dual-plasticizer engineering with CO_(2)-based polymers,offers insights for designing high-performance,eco-friendly lithium metal batteries.展开更多
Rechargeable aqueous zinc-ion batteries(AZIBs)exhibit appreciable potential in the domain of electrochemical energy storage.However,there are serious challenges for AZIBs,for instance zinc dendrite growth,hydrogen evo...Rechargeable aqueous zinc-ion batteries(AZIBs)exhibit appreciable potential in the domain of electrochemical energy storage.However,there are serious challenges for AZIBs,for instance zinc dendrite growth,hydrogen evolution reaction(HER),and corrosion side reactions.Herein,we propose a surface engineering modification strategy for coating the montmorillonite(MMT)layer onto the surface of the Zn anode to tackle these issues,thereby achieving high cycling stability for rechargeable AZIBs.The results reveal that the MMT layer on the surface of the Zn anode is able to provide ordered zincophilic channels for zinc ions migration,facilitating the reaction kinetics of zinc ions.Density functional theory(DFT)calculations and water contact angle(CA)tests prove that MMT@Zn anode exhibits superior adsorption capacity for Zn^(2+)and better hydrophobicity than the bare Zn anode,thereby achieving excellent cycling stability.Moreover,the MMT@Zn||MMT@Zn symmetric cell holds the stable cycling over 5600 h at 0.5 mA cm^(-2)and 0.125 m A h cm^(-2),even exceeding 1800 h long cycling under harsh conditions of 5 m A cm^(-2)and 1.25 m A h cm^(-2).The MMT@Zn||V_(2)O_(5)full cell reaches over 3000 cycles at 2 A g^(-1)with excellent rate capability.Therefore,this surface engineering modification strategy for enhancing the electrochemical performance of AZIBs represents a promising application.展开更多
Lithium niobate(LN)has remained at the forefront of academic research and industrial applications due to its rich material properties,which include second-order nonlinear optic,electro-optic,and piezoelectric properti...Lithium niobate(LN)has remained at the forefront of academic research and industrial applications due to its rich material properties,which include second-order nonlinear optic,electro-optic,and piezoelectric properties.A further aspect of LN’s versatility stems from the ability to engineer ferroelectric domains with micro and even nano-scale precision in LN,which provides an additional degree of freedom to design acoustic and optical devices with improved performance and is only possible in a handful of other materials.In this review paper,we provide an overview of the domain engineering techniques developed for LN,their principles,and the typical domain size and pattern uniformity they provide,which is important for devices that require high-resolution domain patterns with good reproducibility.It also highlights each technique's benefits,limitations,and adaptability for an application,along with possible improvements and future advancement prospects.Further,the review provides a brief overview of domain visualization methods,which is crucial to gain insights into domain quality/shape and explores the adaptability of the proposed domain engineering methodologies for the emerging thin-film lithium niobate on an insulator platform,which creates opportunities for developing the next generation of compact and scalable photonic integrated circuits and high frequency acoustic devices.展开更多
Lattice-strain engineering has demonstrated its capability to influence the electronic structure and catalytic performance of electrocatalysts.Herein,we present a facile method for inducing thermal strain in cobalt/mo...Lattice-strain engineering has demonstrated its capability to influence the electronic structure and catalytic performance of electrocatalysts.Herein,we present a facile method for inducing thermal strain in cobalt/molybdenum nitride rod-shaped structures(denoted Co/Mo_(2)N)via ammonia-assisted reduction,which effectively modulating the HER performance.The optimized Co/Mo_(2)N-500,characterized by 3%tensile lattice strain,demonstrates exceptional HER activity with lower overpotentials of140 mV and 184 mV at high current density of 1000 mA cm^(-2)in alkaline freshwater and seawater electrolytes,respectively.Co/Mo_(2)N also exhibits excellent long-term durability even at a high current density of 300 mA cm^(-2),surpassing its counterparts and benchmark Pt/C catalyst.Density functional theory calculations validate that the tensile strain optimizes the d-band states,water dissociation,and hydrogen adsorption kinetics of the strained Mo_(2)N in Co/Mo_(2)N,thereby improving its catalytic efficacy.This work provides valuable insights into controlling lattice strain to develop highly efficient electrocatalysts towards advanced electrocatalytic applications.展开更多
Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceram...Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceramic fillers.Here,a host–guest inversion engineering strategy is proposed to develop superionic CSEs using cost-effective SiO_(2) nanoparticles as passive ceramic hosts and poly(vinylidene fluoride-hexafluoropropylene)(PVH)microspheres as polymer guests,forming an unprecedented“polymer guest-in-ceramic host”(i.e.,PVH-in-SiO_(2))architecture differing from the traditional“ceramic guest-in-polymer host”.The PVH-in-SiO_(2) exhibits excellent Li-salt dissociation,achieving high-concentration free Li+.Owing to the low diffusion energy barriers and high diffusion coefficient,the free Li+is thermodynamically and kinetically favorable to migrate to and transport at the SiO_(2)/PVH interfaces.Consequently,the PVH-in-SiO_(2) delivers an exceptional ionic conductivity of 1.32.10−3 S cm−1 at 25℃(vs.typically 10−5–10−4 S cm−1 using high-cost active ceramics),achieved under an ultralow residual solvent content of 2.9 wt%(vs.8–15 wt%in other CSEs).Additionally,PVH-in-SiO_(2) is electrochemically stable with Li anode and various cathodes.Therefore,the PVH-in-SiO_(2) demonstrates excellent high-rate cyclability in LiFePO4|Li full cells(92.9%capacity-retention at 3C after 300 cycles under 25℃)and outstanding stability with high-mass-loading LiFePO4(9.2 mg cm−1)and high-voltage NCM622(147.1 mAh g−1).Furthermore,we verify the versatility of the host–guest inversion engineering strategy by fabricating Na-ion and K-ion-based PVH-in-SiO_(2) CSEs with similarly excellent promotions in ionic conductivity.Our strategy offers a simple,low-cost approach to fabricating superionic CSEs for large-scale application of solid-state Li metal batteries and beyond.展开更多
基金Supported by the Shanghai Rising Star Program (Grant No. 21QB1403900)the Shanghai Municipal Commission of Science and Technology (Grant No. 22170712600)。
文摘Knowing the optimal operating parameters of Stirling engines is important for efficient combustion through adaptability to changed pressures and oxygen atmospheres. In this study, the optimum operating conditions for efficient combustion in a singular Stirling engine combustor at different oxygen atmospheres were investigated and determined. Numerical simulations were performed to investigate the effects of ejection ratio and pressure on combustion performance. In an oxygen/carbon dioxide atmosphere, the results show that increasing the ejection ratio substantially alters the flame distribution in the Stirling engine combustor, increasing heat transfer and external combustion efficiency. In contrast, increasing the ejection ratio reduces the average and maximum temperatures of the Stirling engine combustor. Increased pressure affects the flame distribution in the Stirling engine combustor and impedes the flow and convective heat transfer in the combustor, reducing the overall external combustion efficiency at pressures above 6.5 MPa. In an air/carbon dioxide atmosphere, an increased ejection ratio reduces the average and maximum temperatures in the Stirling engine combustor. However, the overall flame distribution does not change substantially. The external combustion efficiency tends to increase and then decrease because of two opposing factors: the increase in the convective heat transfer coefficient and the decrease in the temperature difference. Increasing pressure inhibits forced convection heat transfer in the Stirling engine combustor, reducing external combustion efficiency, which drops from 78% to 65% when pressure increases from 0.2 MPa to 0.5 MPa.
基金supported by the National Natural Science Foundation of China(U21A20281)the Special Fund for Young Teachers from Zhengzhou University(JC23557030,JC23257011)+1 种基金the Key Research Projects of Higher Education Institutions of Henan Province(24A530009)the Project of Zhongyuan Critical Metals Laboratory(GJJSGFYQ202336).
文摘Point defect engineering endows catalysts with novel physical and chemical properties,elevating their electrocatalytic efficiency.The introduction of defects emerges as a promising strategy,effectively modifying the electronic structure of active sites.This optimization influences the adsorption energy of intermediates,thereby mitigating reaction energy barriers,altering paths,enhancing selectivity,and ultimately improving the catalytic efficiency of electrocatalysts.To elucidate the impact of defects on the electrocatalytic process,we comprehensively outline the roles of various point defects,their synthetic methodologies,and characterization techniques.Importantly,we consolidate insights into the relationship between point defects and catalytic activity for hydrogen/oxygen evolution and CO_(2)/O_(2)/N_(2) reduction reactions by integrating mechanisms from diverse reactions.This underscores the pivotal role of point defects in enhancing catalytic performance.At last,the principal challenges and prospects associated with point defects in current electrocatalysts are proposed,emphasizing their role in advancing the efficiency of electrochemical energy storage and conversion materials.
基金supported by the National Natural Science Foundation of China(Grant Nos.52272103 and 52072010)Beijing Natural Science Foundation(Grant Nos.2242029 and JL23004).
文摘High temperature piezoelectric energy harvester(HTPEH)is an important solution to replace chemical battery to achieve independent power supply of HT wireless sensors.However,simultaneously excellent performances,including high figure of merit(FOM),insulation resistivity(ρ)and depolarization temperature(Td)are indispensable but hard to achieve in lead-free piezoceramics,especially operating at 250°C has not been reported before.Herein,well-balanced performances are achieved in BiFeO3–BaTiO3 ceramics via innovative defect engineering with respect to delicate manganese doping.Due to the synergistic effect of enhancing electrostrictive coefficient by polarization configuration optimization,regulating iron ion oxidation state by high valence manganese ion and stabilizing domain orientation by defect dipole,comprehensive excellent electrical performances(Td=340°C,ρ250°C>10^(7)Ωcm and FOM_(250°C)=4905×10^(–15)m^(2)N^(−1))are realized at the solid solubility limit of manganese ions.The HT-PEHs assembled using the rationally designed piezoceramic can allow for fast charging of commercial electrolytic capacitor at 250°C with high energy conversion efficiency(η=11.43%).These characteristics demonstrate that defect engineering tailored BF-BT can satisfy high-end HT-PEHs requirements,paving a new way in developing selfpowered wireless sensors working in HT environments.
基金support of the National Natural Science Foundation of China(Grant No.22225801,22178217 and 22308216)supported by the Fundamental Research Funds for the Central Universities,conducted at Tongji University.
文摘Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.
基金National Natural Science Foundation of China (62104061, 62074052, 61974173 and 52072327)。
文摘Solution-processed Cu(In,Ga)Se_(2)(CIGS) solar cells suffer from serious carrier recombination and power conversion efficiency(PCE) loss because of the poor film properties and easy formation of defects.Herein, we propose Ag&Se co-selenization strategy to enhance the crystallization and passivate harmful defects of the CIGS films. The formation of Ag-Se phase during the selenization process enables the formation of large grains and suppresses the deep level defects. It is found that Ag doping can enlarge the depletion region width, lower the Urbach energy and prolong the carrier lifetime. As a result, a champion solution-processed CIGS solar cell presents a high efficiency of 16.48% with the highly improved opencircuit voltage(VOC) of 662 m V and fill factor(FF) of 75.8%. This work provides an efficient strategy to prepare high quality solution-processed CIGS films for high-performance CIGS solar cells.
基金the financial support from the Guangxi Natural Science Foundation(grant no.2021GXNSFDA075012,2023GXNSFGA026002)National Natural Science Foundation of China(52104298,22075073,52362027,52462029)Fundamental Research Funds for the Central Universities(531107051077).
文摘Stress accumulation is a key factor leading to sodium storage performance deterioration for NiSe_(2)-based anodes.Therefore,inhibiting the concentrated local stress during the sodiataion/desodiation process is crucial for acquiring stable NiSe2-based materials for sodium-ion batteries(SIBs),Herein,a stress dissipation strategy driven by architecture engineering is proposed,which can achieve ultrafast and ultralong sodium storage properties.Different from the conventional sphere-like or rod-like architecture,the three-dimensional(3D)flower-like NiSe_(2)@C composite is delicately designed and assembled with onedimensional nanorods and carbon framework.More importantly,the fundamental mechanism of improved structure stability is unveiled by simulations and experimental results simultaneously.It demonstrates that this designed multidimensional flower-like architecture with dispersed nanorods can balance the structural mismatch,avoid concentrated local strain,and relax the internal stress,mainly induced by the unavoidable volume variation during the repeated conversion processes.Moreover,it can provide more Na^(+)-storage sites and multi-directional migration pathways,leading to a fast Na^(+)-migration channel with boosted reaction kinetic.As expected,it delivers superior rate performance(441 mA h g^(-1)at 5.0 A g^(-1))and long cycling stability(563 mA h g^(-1)at 1.0 A g^(-1)over 1000 cycles)for SIBs.This work provides useful insights for designing high-performance conversion-based anode materials for SIBs.
基金supported by the National Key Research Program of China(Y91Z0152B4,2018YFA0703501)the National Nature Science Foundation of China(22172173,22021002)。
文摘Finding ways to produce dense and smooth perovskite films with negligible defects is vital for achieving high-efficiency perovskite solar cells(PSCs).Herein,we aim to enhance the quality of the perovskite films through the utilization of a multifunctional additive in the perovskite anti-solvent,a strategy referred to as anti-solvent additive engineering.Specifically,we introduce ortho-substituted-4′-(4,4″-di-tertbutyl-1,1′:3′,1″-terphenyl)-graphdiyne(o-TB-GDY)as an AAE additive,characterized by its sp/sp^2-cohybridized and highlyπ-conjugated structure,into the anti-solvent.o-TB-GDY not only significantly passivates undercoordinated lead defects(through potent coordination originating from specific highπ–electron conjugation),but also serves as nucleation seeds to effectively enhance the nucleation and growth of perovskite crystals.This markedly reduces defects and non-radiative recombination,thereby increasing the power conversion efficiency(PCE)to 25.62%(certified as 25.01%).Meanwhile,the PSCs exhibit largely enhanced stability,maintaining 92.6%of their initial PCEs after 500 h continuous 1-sun illumination at~23°C in a nitrogen-filled glove box.
基金financially supported by the National Natural Science Foundation of China(52162036 and 22378342)Key Project of Nature Science Foundation of Xinjiang(2021D01D08)+2 种基金Major Projects of Xinjiang(2022A01005-4 and 2021A01001-1)Key Research and Development Project of Xinjiang(2023B01025-1)the support from the Doctoral Student Special Program of the Young Talents Support Project of the China Association for Science and Technology in 2024。
文摘Practical Zn metal batteries have been hindered by several challenges,including Zn dendrite growth,undesirable side reactions,and unstable electrode/electrolyte interface.These issues are particularly more serious in low-concentration electrolytes.Herein,we design a Zn salt-mediated electrolyte with in situ ring-opening polymerization of the small molecule organic solvent.The Zn(TFSI)_(2)salt catalyzes the ring-opening polymerization of(1,3-dioxolane(DOL)),generating oxidation-resistant and non-combustible long-chain polymer(poly(1,3-dioxolane)(pDOL)).The pDOL reduces the active H_(2)O molecules in electrolyte and assists in forming stable organic–inorganic gradient solid electrolyte interphase with rich organic constituents,ZnO and ZnF_(2).The introduction of pDOL endows the electrolyte with several advantages:excellent Zn dendrite inhibition,improved corrosion resistance,widened electrochemical window(2.6 V),and enhanced low-temperature performance(freezing point=-34.9°C).Zn plating/stripping in pDOL-enhanced electrolyte lasts for 4200 cycles at 99.02%Coulomb efficiency and maintains a lifetime of 8200 h.Moreover,Zn metal anodes deliver stable cycling for 2500 h with a high Zn utilization of 60%.A Zn//VO_(2)pouch cell assembled with lean electrolyte(electrolyte/capacity(E/C=41 mL(Ah)^(-1))also demonstrates a capacity retention ratio of 92%after 600 cycles.These results highlight the promising application prospects of practical Zn metal batteries enabled by the Zn(TFSI)2-mediated electrolyte engineering.
基金support from the National Key Research and Development Program of China(2022YFE0206000)the National Natural Science Foundation of China(U2001219,51973064)+3 种基金the Guangdong Basic and Applied Basic Research Foundation(2023B1515040003,2024A1515010262)the Natural Science Foundation of Guangdong Province(2023B1212060003)the Open Project Program of Wuhan National Laboratory for Optoelectronics(NO.2021WNLOKF014)the State Key Lab of Luminescent Materials and Devices,South China University of Technology(Skllmd-2023-05).
文摘Formamidinium lead bromide(FAPbBr_(3))perovskite nanocrystals(NCs)are promising for display and lighting due to their ultra-pure green emission.However,the thermal quenching will exacerbate their performance degradation in practical applications,which is a common issue for halide perovskites.Here,we reported the heat-resistant FAPbBr_(3)NCs prepared by a ligand-engineered room-temperature synthesis strategy.An aromatic amine,specificallyβ-phenylethylamine(PEA)or 3-fluorophenylethylamine(3-F-PEA),was incoporated as the short-chain ligand to expedite the crystallization rate and control the size distribution of FAPbBr_(3)NCs.Employing this ligand engineering approach,we synthesized high quality FAPbBr_(3)NCs with uniform grain size and reduced long-chain alkyl ligands,resulting in substantially suppressed thermal quenching and enhanced carrier transportation in the perovskite NCs films.Most notably,more than 90%of the room temperature PL intensity in the 3-F-PEA modified FAPbBr_(3)NCs film was preserved at 380 K.Consequently,we fabricated ultra-pure green EL devices with a room temperature external quantum efficiency(EQE)as high as 21.9%at the luminance of above 1,000 cd m^(-2),and demonstrated less than 10%loss in EQE at 343 K.This study introduces a novel room temperature method to synthesize efficient FAPbBr_(3)NCs with exceptional thermal stability,paving the way for advanced optoelectronic device applications.
基金supported by the National Key R&D Program of China(2022YFE0118400)the National Natural Science Foundation of China(6217520)+1 种基金the Science and Technology Project of Fujian Province of China(2021H6018)the Natural Science Foundation of Fujian Province of China(2021J06009)。
文摘Flexible perovskite solar cells(fPSCs)have demonstrated commercial viability because of their promising lightness,flexibility,and low-cost advantages.However,in most applications,the fPSCs suffer from constant external stress,such as being kept at a convex bending state,imposing external stress on the brittle perovskite films and causing the fPSCs long-term stability problems.Overcoming these issues is vital.Herein,we propose an effective way to enhance the stability of the fPSCs under convex bending by modulating the residual stress of perovskite film for the first time.Specifically,we have carefully designed a synergistic strain engineering to toughen the perovskite films by introducing 1-butyl-3-methylimidazolium tetrafluoroborate,citric acid,and a novel cross-linker,5-(1,2-dithiolan-3-yl)pentanoate into perovskite films simultaneously.Besides passivating the perovskite films,the multiple additives effectively convert the residual stress within the perovskite films from tensile to compressive type to alleviate the detrimental impact of bending on the flexible perovskite films.As a result,the optimal efficiencies of triple-additive modified fPSCs have achieved 22.19%(0.06 cm^(2))and 19.44%(1.02 cm^(2)).More importantly,the strategy could significantly improve the stability of the perovskite films and fPSCs at a convex bending state.Our approach is inductive for the future practical field applications of high-performance fPSCs.
文摘The ability to replicate the microenvironment of the human body through the fabrication of scaffolds is a significant achievement in the biomedical field.However,the search for the ideal scaffold is still in its infancy and there are significant challenges to overcome.In the modern era,the scientific community is increasingly turned to natural substances due to their superior biological ability,lower cost,biodegradability,and lower toxicity than synthetic lab-made products.Chitosan is a well-known polysaccharide that has recently garnered a high amount of attention for its biological activities,especially in 3D bone tissue engineering.Chitosan closely matches the native tissues and thus stands out as a popular candidate for bioprinting.This review focuses on the potential of chitosan-based scaffolds for advancements and the drawbacks in bone treatment.Chitosan-based nanocomposites have exhibited strong mechanical strength,water-trapping ability,cellular interaction,and biodegradability.Chitosan derivatives have also encouraged and provided different routes for treatment and enhanced biological activities.3D tailored bioprinting has opened new doors for designing and manufacturing scaffolds with biological,mechanical,and topographical properties.
基金support from the Scientific Research Fund of Zhejiang Provincial Education Department(Y202353855)the Zhejiang Provincial Key R&D Project(2021C01056)+1 种基金the Programme of Introducing Talents of Discipline to Universities(No.D17008)the National Natural Science Foundation of China(22208312).
文摘Three large π-conjugated and imine-based COFs,named TFP-TAB,TFP-TTA,and TTA-TTB,were synthesized via the ordered incorporation of benzene and triazine rings in the same host framework to study how the structural units affect the efficiency of CO_(2)photoreduction.Results from both experiments and density-functional theory(DFT)calculations indicate the separation and transfer of the photoinduced charges is highly related to the triazine-N content and the conjugation degree in the skeletons of COFs.High-efficiency CO_(2)photoreduction can be achieved by rationally adjusting the number and position of both benzene and triazine rings in the COFs.Specifically,TTA-TTB,with orderly interlaced triazine-benzene heterojunctions,can suppress the recombination probability of electrons and holes,which effectively immobilizes the key species(COOH)and lowers the free energy change of the potential-determining step,and thus exhibits a superior visible-light-induced photocatalytic activity that yields 121.7 μmol HCOOH g^(-1)h^(-1).This research,therefore,helps to elucidate the effects of the different structural blocks in COFs on inherent heterogeneous photocatalysis for CO_(2)reduction at a molecular level.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB2502200)the National Natural Science Foundation of China(Grant Nos.52325207,22239003,and 22393904).
文摘Lithium-rich manganese-based cathodes(LRMs)have garnered significant attention as promising candidates for highenergy-density batteries due to their exceptional specific capacity exceeding 300 mAh/g,achieved through synergistic anionic and cationic redox reactions.However,these materials face challenges including oxygen release-induced structural degradation and consequent capacity fading.To address these issues,strategies such as surface modification and bulk phase engineering have been explored.In this study,we developed a facile and cost-effective quenching approach that simultaneously modifies both surface and bulk characteristics.Multi-scale characterization and computational analysis reveal that rapid cooling partially preserves the high-temperature disordered phase in the bulk structure,thereby enhancing the structural stability.Concurrently,Li^(+)/H^(+)exchange at the surface forms a robust rock-salt/spinel passivation layer,effectively suppressing oxygen evolution and mitigating interfacial side reactions.This dual modification strategy demonstrates a synergistic stabilization effect.The enhanced oxygen redox activity coexists with the improved structural integrity,leading to superior electrochemical performance.The optimized cathode delivers an initial discharge capacity approaching 307.14 mAh/g at 0.1 C and remarkable cycling stability with 94.12%capacity retention after 200 cycles at 1 C.This study presents a straightforward and economical strategy for concurrent surface–bulk modification,offering valuable insights for designing high-capacity LRM cathodes with extended cycle life.
基金supported by the National Key Research and Development Program(2019YFA0705701)National Natural Science Foundation of China(22075329,22008267,21978332 and 22179149)+1 种基金Research and Development Project of Henan Academy Sciences China(232018002)Guangdong Basic and Applied Basic Research Foundation(2021A1515010731)。
文摘One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible phases.Nevertheless,the regulation of intermolecular interactions between plasticizers and rigid and flexible phases has been largely overlooked.Here,an intermolecular interaction engineering strategy is carried out with well-chosen dual-plasticize within qua si-sol id-state polymer electrolytes(QSPEs).Succinonitrile exhibits a stronger affinity towards rigid phase hydrogenated nitrile butadiene rubber(HNBR),while propene carbonate demonstrates a stronger affinity towards flexible segments poly(propylene carbonate)(PPC).This tailored intermolecular interaction engineering allows for differential plasticization of the polymer's rigid and flexible phases,thereby achieving a balance between ionic conductivity and mechanical strength.The QSPE have both higher ionic conductivity(1.04×10^(-4)S cm^(-1)at 30℃),t_(Li+)(0.55),and tensile strength(0.76 MPa).Li//Li symmetric cells maintaining performance over1100 h at 0.1 mA cm^(-2)and Li//LiFePO_(4)cells retaining 85.0%capacity after 700 cycles at 1.0 C.It is a unique angle to employ intermolecular interaction engineering in QSPEs through dual-plasticizer approach combined with CO_(2)-based polymer materials.This sustainable strategy combining dual-plasticizer engineering with CO_(2)-based polymers,offers insights for designing high-performance,eco-friendly lithium metal batteries.
基金National Natural Science Foundation of China(Grant No.22005318,22379152)Western Young Scholars Foundations of Chinese Academy of Sciences+4 种基金Lanzhou Youth Science and Technology Talent Innovation Project(Grant No.2023-NQ-86,No.2023-QN-96)Lanzhou Chengguan District Science and Technology Plan Project(Grant No.2023-rc-4,2022-rc-4)Collaborative Innovation Alliance Fund for Young Science and Technology Worker(Grant No.HZJJ23-7)National Nature Science Foundations of Gansu Province(Grant No.21JR11RA020)Fundamental Research Funds for the Central Universities(Grant No.31920220073,31920230128)。
文摘Rechargeable aqueous zinc-ion batteries(AZIBs)exhibit appreciable potential in the domain of electrochemical energy storage.However,there are serious challenges for AZIBs,for instance zinc dendrite growth,hydrogen evolution reaction(HER),and corrosion side reactions.Herein,we propose a surface engineering modification strategy for coating the montmorillonite(MMT)layer onto the surface of the Zn anode to tackle these issues,thereby achieving high cycling stability for rechargeable AZIBs.The results reveal that the MMT layer on the surface of the Zn anode is able to provide ordered zincophilic channels for zinc ions migration,facilitating the reaction kinetics of zinc ions.Density functional theory(DFT)calculations and water contact angle(CA)tests prove that MMT@Zn anode exhibits superior adsorption capacity for Zn^(2+)and better hydrophobicity than the bare Zn anode,thereby achieving excellent cycling stability.Moreover,the MMT@Zn||MMT@Zn symmetric cell holds the stable cycling over 5600 h at 0.5 mA cm^(-2)and 0.125 m A h cm^(-2),even exceeding 1800 h long cycling under harsh conditions of 5 m A cm^(-2)and 1.25 m A h cm^(-2).The MMT@Zn||V_(2)O_(5)full cell reaches over 3000 cycles at 2 A g^(-1)with excellent rate capability.Therefore,this surface engineering modification strategy for enhancing the electrochemical performance of AZIBs represents a promising application.
基金supported by the Australian Research Council Centre of Excellence in Optical Microcombs for Breakthrough Science COMBS(CE230100006)the Australian Research Council grants DP220100488 and DE230100964funded by the Australian Government.
文摘Lithium niobate(LN)has remained at the forefront of academic research and industrial applications due to its rich material properties,which include second-order nonlinear optic,electro-optic,and piezoelectric properties.A further aspect of LN’s versatility stems from the ability to engineer ferroelectric domains with micro and even nano-scale precision in LN,which provides an additional degree of freedom to design acoustic and optical devices with improved performance and is only possible in a handful of other materials.In this review paper,we provide an overview of the domain engineering techniques developed for LN,their principles,and the typical domain size and pattern uniformity they provide,which is important for devices that require high-resolution domain patterns with good reproducibility.It also highlights each technique's benefits,limitations,and adaptability for an application,along with possible improvements and future advancement prospects.Further,the review provides a brief overview of domain visualization methods,which is crucial to gain insights into domain quality/shape and explores the adaptability of the proposed domain engineering methodologies for the emerging thin-film lithium niobate on an insulator platform,which creates opportunities for developing the next generation of compact and scalable photonic integrated circuits and high frequency acoustic devices.
基金supported by the Hunan Joint International Laboratory of Advanced Materials and Technology for Clean Energy(2020CB1007)Fundamental Research Funds for the Central Universities and Guangxi Key Laboratory of Information Materials and Guilin University of Electronic Technology,China(231002-K)+4 种基金Natural Science Foundation of Guangxi Zhuang Autonomous Region(2022GXNSFAA035467)Guangxi Science and Technology Program(Guike AD21220067)National Natural Science Foundation of China(22369002)Nationally Funded Postdoctoral Researcher Program(GZC20230756)China Postdoctoral Science Foundation(2024M750858)。
文摘Lattice-strain engineering has demonstrated its capability to influence the electronic structure and catalytic performance of electrocatalysts.Herein,we present a facile method for inducing thermal strain in cobalt/molybdenum nitride rod-shaped structures(denoted Co/Mo_(2)N)via ammonia-assisted reduction,which effectively modulating the HER performance.The optimized Co/Mo_(2)N-500,characterized by 3%tensile lattice strain,demonstrates exceptional HER activity with lower overpotentials of140 mV and 184 mV at high current density of 1000 mA cm^(-2)in alkaline freshwater and seawater electrolytes,respectively.Co/Mo_(2)N also exhibits excellent long-term durability even at a high current density of 300 mA cm^(-2),surpassing its counterparts and benchmark Pt/C catalyst.Density functional theory calculations validate that the tensile strain optimizes the d-band states,water dissociation,and hydrogen adsorption kinetics of the strained Mo_(2)N in Co/Mo_(2)N,thereby improving its catalytic efficacy.This work provides valuable insights into controlling lattice strain to develop highly efficient electrocatalysts towards advanced electrocatalytic applications.
基金financial support from the National Natural Science Foundation of China(Nos.52250010 and 52201242)the 261 Project of MIIT,Natural Science Foundation of Jiangsu Province(No.BK20240179)the Young Elite Scientists Sponsorship Program by CAST(No.2021QNRC001).
文摘Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceramic fillers.Here,a host–guest inversion engineering strategy is proposed to develop superionic CSEs using cost-effective SiO_(2) nanoparticles as passive ceramic hosts and poly(vinylidene fluoride-hexafluoropropylene)(PVH)microspheres as polymer guests,forming an unprecedented“polymer guest-in-ceramic host”(i.e.,PVH-in-SiO_(2))architecture differing from the traditional“ceramic guest-in-polymer host”.The PVH-in-SiO_(2) exhibits excellent Li-salt dissociation,achieving high-concentration free Li+.Owing to the low diffusion energy barriers and high diffusion coefficient,the free Li+is thermodynamically and kinetically favorable to migrate to and transport at the SiO_(2)/PVH interfaces.Consequently,the PVH-in-SiO_(2) delivers an exceptional ionic conductivity of 1.32.10−3 S cm−1 at 25℃(vs.typically 10−5–10−4 S cm−1 using high-cost active ceramics),achieved under an ultralow residual solvent content of 2.9 wt%(vs.8–15 wt%in other CSEs).Additionally,PVH-in-SiO_(2) is electrochemically stable with Li anode and various cathodes.Therefore,the PVH-in-SiO_(2) demonstrates excellent high-rate cyclability in LiFePO4|Li full cells(92.9%capacity-retention at 3C after 300 cycles under 25℃)and outstanding stability with high-mass-loading LiFePO4(9.2 mg cm−1)and high-voltage NCM622(147.1 mAh g−1).Furthermore,we verify the versatility of the host–guest inversion engineering strategy by fabricating Na-ion and K-ion-based PVH-in-SiO_(2) CSEs with similarly excellent promotions in ionic conductivity.Our strategy offers a simple,low-cost approach to fabricating superionic CSEs for large-scale application of solid-state Li metal batteries and beyond.
