Direct air capture(DAC)of CO_(2)plays an indispensable role in achieving carbon-neutral goals as one of the key negative emission technologies.Since large air flows are required to capture the ultradilute CO_(2)from t...Direct air capture(DAC)of CO_(2)plays an indispensable role in achieving carbon-neutral goals as one of the key negative emission technologies.Since large air flows are required to capture the ultradilute CO_(2)from the air,lab-synthesized adsorbents in powder form may cause unacceptable gas pressure drops and poor heat and mass transfer efficiencies.A structured adsorbent is essential for the implementation of gas-solid contactors for cost-and energy-efficient DAC systems.In this study,efficient adsorbent poly(ethyleneimine)(PEI)-functionalized Mg-Al-CO_(3)layered double hydroxide(LDH)-derived mixed metal oxides(MMOs)are three-dimensional(3D)printed into monoliths for the first time with more than 90%adsorbent loadings.The printing process has been optimized by initially printing the LDH powder into monoliths followed by calcination into MMO monoliths.This structure exhibits a 32.7%higher specific surface area and a 46.1%higher pore volume,as compared to the direct printing of the MMO powder into a monolith.After impregnation of PEI,the monolith demonstrates a large adsorption capacity(1.82 mmol/g)and fast kinetics(0.7 mmol/g/h)using a CO_(2)feed gas at 400 ppm at 25℃,one of the highest values among the shaped DAC adsorbents.Smearing of the amino-polymers during the post-printing process affects the diffusion of CO_(2),resulting in slower adsorption kinetics of pre-impregnation monoliths compared to post-impregnation monoliths.The optimal PEI/MeOH ratio for the post-impregnation solution prevents pores clogging that would affect both adsorption capacity and kinetics.展开更多
Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact l...Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport.Solid electrolytes are generally studied as two-dimensional(2D)structures with planar interfaces,showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces.Herein,three-dimensional(3D)architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment.Multiple-type electrolyte films with vertical-aligned micro-pillar(p-3DSE)and spiral(s-3DSE)structures are rationally designed and developed,which can be employed for both Li metal anode and cathode in terms of accelerating the Li+transport within electrodes and reinforcing the interfacial adhesion.The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm^(−2).The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm^(−2)(LFP)and 3.92 mAh cm^(−2)(NCM811).This unique design provides enhancements for both anode and cathode electrodes,thereby alleviating interfacial degradation induced by dendrite growth and contact loss.The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.展开更多
At present,commercial Li-ion batteries are hardly to satisfy the growing demand for high energy density,for this purpose,lithium metal batteries have attracted worldwide attention in recent years.However,its practical...At present,commercial Li-ion batteries are hardly to satisfy the growing demand for high energy density,for this purpose,lithium metal batteries have attracted worldwide attention in recent years.However,its practical applications are hindered by the formation of Li dendrites and volume effect during Li plating/stripping process,which leads to a lot of safety hazards.Herein,we first employed MOF-derived V_(2)O_(5) nanoparticles to decorate the carbon fiber cloth(CFC)backbone to acquire a lithiophilic 3D porous conductive framework(CFC@V_(2)O_(5)).Subsequently,the CFC@V_(2)O_(5) skeleton was permeated with molten Li to prepare CFC@V_(2)O_(5)@Li composite anode.The CFC@V_(2)O_(5)@Li composite anode can be stably cycled for more than 1650 h at high current density(5 mA·cm^(-2))and areal capacity(5 mA·h·cm^(–2)).The prepared full cell can initially maintain a high capacity of about 143 mA·h·g^(-1) even at a high current density of 5 C,and can still maintain 114 mA·h·g^(-1) after 1000 cycles.展开更多
The ripple effect induced by uncontrollable Zn deposition is considered as the Achilles heel for developing high-performance aqueous Zn-ion batteries.For this problem,this work reports a design concept of 3D artificia...The ripple effect induced by uncontrollable Zn deposition is considered as the Achilles heel for developing high-performance aqueous Zn-ion batteries.For this problem,this work reports a design concept of 3D artificial array interface engineering to achieve volume stress elimination,preferred orientation growth and dendrite-free stable Zn metal anode.The mechanism of MXene array interface on modulating the growth kinetics and deposition behavior of Zn atoms were firstly disclosed on the multi-scale level,including the in-situ optical microscopy and transient simulation at the mesoscopic scale,in-situ Raman spectroscopy and in-situ X-ray diffraction at the microscopic scale,as well as density functional theory calculation at the atomic scale.As indicated by the electrochemical performance tests,such engineered electrode exhibits the comprehensive enhancements not only in the resistance of corrosion and hydrogen evolution,but also the rate capability and cyclic stability.High-rate performance(20 mA cm^(-2))and durable cycle lifespan(1350 h at 0.5 mA cm^(-2),1500 h at 1 mA cm^(-2)and 800 h at 5 mA cm^(-2))can be realized.Moreover,the improvement of rate capability(214.1 mAh g^(-1)obtained at 10 A g^(-1))and cyclic stability also can be demonstrated in the case of 3D MXene array@Zn/VO2battery.Beyond the previous 2D closed interface engineering,this research offers a unique 3D open array interface engineering to stabilize Zn metal anode,the controllable Zn deposition mechanism revealed is also expected to deepen the fundamental of rechargeable batteries including but not limited to aqueous Zn metal batteries.展开更多
Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline H...Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline HER kinetics.Here,we design ternary transition metals-based nickel telluride(Mo WNi Te)catalysts consisting of high valence non-3d Mo and W metals and oxophilic Te as a first demonstration of non-precious heterogeneous electrocatalysts following the bifunctional mechanism.The Mo WNi Te showed excellent HER catalytic performance with overpotentials of 72,125,and 182 mV to reach the current densities of 10,100,and 1000 mA cm^(-2),respectively,and the corresponding Tafel slope of 47,52,and 58 mV dec-1in alkaline media,which is much superior to commercial Pt/C.Additionally,the HER performance of Mo WNi Te is well maintained up to 3000 h at the current density of 100 mA cm^(-2).It is further demonstrated that the Mo WNi Te exhibits remarkable HER activities with an overpotential of 45 mV(31 mV)and Tafel slope of 60 mV dec-1(34 mV dec-1)at 10 mA cm^(-2)in neutral(acid)media.The superior HER performance of Mo WNi Te is attributed to the electronic structure modulation,inducing highly active low valence states by the incorporation of high valence non-3d transition metals.It is also attributed to the oxophilic effect of Te,accelerating water dissociation kinetics through a bifunctional catalytic mechanism in alkaline media.Density functional theory calculations further reveal that such synergistic effects lead to reduced free energy for an efficient water dissociation process,resulting in remarkable HER catalytic performances within universal pH environments.展开更多
Three-dimensional-structured metal oxides have myriad applications for optoelectronic devices.Comparing to conventional lithography-based manufacturing methods which face significant challenges for 3D device architect...Three-dimensional-structured metal oxides have myriad applications for optoelectronic devices.Comparing to conventional lithography-based manufacturing methods which face significant challenges for 3D device architectures,additive manufacturing approaches such as direct ink writing offer convenient,on-demand manufacturing of 3D oxides with high resolutions down to sub-micrometer scales.However,the lack of a universal ink design strategy greatly limits the choices of printable oxides.Here,a universal,facile synthetic strategy is developed for direct ink writable polymer precursor inks based on metal-polymer coordination effect.Specifically,polyethyleneimine functionalized by ethylenediaminetetraacetic acid is employed as the polymer matrix for adsorbing targeted metal ions.Next,glucose is introduced as a crosslinker for endowing the polymer precursor inks with a thermosetting property required for 3D printing via the Maillard reaction.For demonstrations,binary(i.e.,ZnO,CuO,In_(2)O_(3),Ga_(2)O_(3),TiO_(2),and Y_(2)O_(3)) and ternary metal oxides(i.e.,BaTiO_(3) and SrTiO_(3)) are printed into 3D architectures with sub-micrometer resolution by extruding the inks through ultrafine nozzles.Upon thermal crosslinking and pyrolysis,the 3D microarchitectures with woodpile geometries exhibit strong light-matter coupling in the mid-infrared region.The design strategy for printable inks opens a new pathway toward 3D-printed optoelectronic devices based on functional oxides.展开更多
This study presents a novel process for the fabrication of metal-intermetallic composites with a 3D bicontinuous structure, achieved through a combination of liquid metal dealloying(LMD) and subsequent alloying. Initi...This study presents a novel process for the fabrication of metal-intermetallic composites with a 3D bicontinuous structure, achieved through a combination of liquid metal dealloying(LMD) and subsequent alloying. Initially, porous Ti structures are produced using the LMD process, followed by immersion in a molten Mg-3Al(wt%) metal. Due to the higher thermodynamic miscibility of Al with Ti compared to Mg, the concentration of Al in the Ti matrix increases as the immersion time increases. This results in a sequential phase transition within the Ti matrix: α-Ti → Ti_(3)Al → Ti Al. The phase transition considerably affects the hardness and strength of the composite material,with the Mg-Ti_(3)Al-Ti Al composite exhibiting a maximum hardness nearly twice as high as that of the conventional Mg-Ti composite. This innovative process holds potential for the development of various bicontinuous metal-intermetallic composites.展开更多
Li metal with high-energy density is considered as the most promising anode for the next-generation rechargeable Li metal batteries;however,the growth of Li dendrites seriously hinders its practical application.Herein...Li metal with high-energy density is considered as the most promising anode for the next-generation rechargeable Li metal batteries;however,the growth of Li dendrites seriously hinders its practical application.Herein,3D free-standing carbon nanofibers modified by lithiophilic metal particles(CNF/Me,Me=Sn,Fe,Co)are obtained in situ by the electrospinning method.Benefiting from the lithophilicity,the CNF/Me composite may effectively prevent the formation of Li dendrites in the Li metal batteries.The optimized CNF/Sn–Li composite electrode exhibits a stable cycle life of over 2350 h during Li plating/stripping.When matched with typical commercial LiFePO_(4)(LFP)cathode,the LFP//CNF/Sn–Li full cell presents a high initial discharge specific capacity of 139 mAh g^(−1)at 1 C,which remains at 146 mAh g^(−1)after 400 cycles.When another state-of-the-art commercial LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM(811))cathode is used,the assembled NCM//CNF/Sn–Li full cell shows a large initial specific discharge capacity of 206 mAh g^(−1)at substantially enhanced 10 C,which keeps at the good capacity of 99 mAh g^(−1)after 300 cycles.These results are greatly superior to the counterparts with Li as the anodes,indicating the great potential for practical utilization of the advanced CNF/Sn–Li electrode.展开更多
Porous and functionally graded materials have seen extensive applications in modern biomedical devices—allowing for improved site-specific performance;their appreciable mechanical,corrosive,and biocompatible properti...Porous and functionally graded materials have seen extensive applications in modern biomedical devices—allowing for improved site-specific performance;their appreciable mechanical,corrosive,and biocompatible properties are highly sought after for lightweight and high-strength load-bearing orthopedic and dental implants.Examples of such porous materials are metals,ceramics,and polymers.Although,easy to manufacture and lightweight,porous polymers do not inherently exhibit the required mechanical strength for hard tissue repair or replacement.Alternatively,porous ceramics are brittle and do not possess the required fatigue resistance.On the other hand,porous biocompatible metals have shown tailorable strength,fatigue resistance,and toughness.Thereby,a significant interest in investigating the manufacturing challenges of porous metals has taken place in recent years.Past research has shown that once the advantages of porous metallic structures in the orthopedic implant industry have been realized,their biological and biomechanical compatibility—with the host bone—has been followed up with extensive methodical research.Various manufacturing methods for porous or functionally graded metals are discussed and compared in this review,specifically,how the manufacturing process influences microstructure,graded composition,porosity,biocompatibility,and mechanical properties.Most of the studies discussed in this review are related to porous structures for bone implant applications;however,the understanding of these investigations may also be extended to other devices beyond the biomedical field.展开更多
Additive manufacturing(AM)is a free-form technology that shows great potential in the integrated creation of three-dimensional(3D)electronics.However,the fabrication of 3D conformal circuits that fulfill the requireme...Additive manufacturing(AM)is a free-form technology that shows great potential in the integrated creation of three-dimensional(3D)electronics.However,the fabrication of 3D conformal circuits that fulfill the requirements of high service temperature,high conductivity and high resolution remains a challenge.In this paper,a hybrid AM method combining the fused deposition modeling(FDM)and hydrophobic treatment assisted laser activation metallization(LAM)was proposed for manufacturing the polyetheretherketone(PEEK)-based 3D electronics,by which the conformal copper patterns were deposited on the 3D-printed PEEK parts,and the adhesion between them reached the 5B high level.Moreover,the 3D components could support the thermal cycling test from-55℃ to 125℃ for more than 100 cycles.Particularly,the application of a hydrophobic coating on the FDM-printed PEEK before LAM can promote an ideal catalytic selectivity on its surface,not affected by the inevitable printing borders and pores in the FDM-printed parts,then making the resolution of the electroless plated copper lines improved significantly.In consequence,Cu lines with width and spacing of only60μm and 100μm were obtained on both as-printed and after-polished PEEK substrates.Finally,the potential of this technique to fabricate 3D conformal electronics was demonstrated.展开更多
The use of commercial products such as a cup and liner for total hip arthroplasty for patients with severe bone defects has a high probability of failure.In these patients the cup alone cannot cover the bone defect,an...The use of commercial products such as a cup and liner for total hip arthroplasty for patients with severe bone defects has a high probability of failure.In these patients the cup alone cannot cover the bone defect,and thus,an additional augment or cage is required.In this study,we designed three-dimensional(3D)printable bone augments as an alternative to surgeries using reinforcement cages.Thirty-five sharp-edged bone augments of various sizes were 3D printed.A biporous structure was designed to reduce the weight of the augment and to facilitate bone ingrowth.Two types of frames were used to prevent damage to the augment’s porous structure and maintain its stability during printing.Furthermore,two types of holes were provided for easy augment fixation at various angles.Fatigue tests were performed on a combination of worst-case sizes derived using finite element analysis.The test results confirmed the structural stability of the specimens at a load of 5340 N.Although the porosity of the specimens was measured to be 63.70%,it cannot be said that the porous nature was uniformly distributed because porosity tests were performed locally and randomly.In summary,3D-printable biporous bone augments capable of bonding from various angles and bidirectionally through angulation and bottom-plane screw holes are proposed.The mechanical results with bone augments indicate good structural safety in patients.However,further research is necessary to study the clinical applications of the proposed bone augment.展开更多
Rational design of porous conductive hosts with high electrical conductivity,large surface area,and adequate interior space is desirable to suppressing dendritic lithium growth and accommodating large volume change of...Rational design of porous conductive hosts with high electrical conductivity,large surface area,and adequate interior space is desirable to suppressing dendritic lithium growth and accommodating large volume change of lithium metal anode during the Li plating/stripping process.However,due to the conductive nature of the conductive hosts,Li is easily deposited directly on the top of the hosts,which hinders it from fully functioning.To circumvent the issue,in this study,we designed a novel porous carbon host with a gradient-pore-size structure based on one-dimensional(1D)carbon with different diameters.With this kind of host,stable cycling with high and stable Coulombic efficiency of~98%is achieved at 0.5 mA cm^(−2) with an areal capacity of 1 mAh cm^(−2) over 320 cycles.In contrast,the normal three-dimensional(3D)carbon nanotube host presents a moss-like Li morphology with wildly fluctuating Coulombic efficiency after 100 cycles.The results reveal that the unique gradient-pore-size structure of the 3D conductive host greatly improves the performance of lithium metal batteries.展开更多
A novel metal matrix composite freeform fabrication approach,fiber traction printing(FTP),is demonstrated through controlling the wetting behavior between fibers and the matrix.This process utilizes the fiber bundle t...A novel metal matrix composite freeform fabrication approach,fiber traction printing(FTP),is demonstrated through controlling the wetting behavior between fibers and the matrix.This process utilizes the fiber bundle to control the cross-sectional shape of the liquid metal,shaping it from circular to rectangular which is more precise.The FTP process could resolve manufacturing difficulties in the complex structure of continuous fiber reinforced metal matrix composites.The printing of the first layer monofilament is discussed in detail,and the effects of the fibrous coating thickness on the mechanical properties and microstructures of the composite are also investigated in this paper.The composite material prepared by the FTP process has a tensile strength of 235.2 MPa,which is close to that of composites fabricated by conventional processes.The complex structures are printed to demonstrate the advantages and innovations of this approach.Moreover,the FTP method is suited to other material systems with good wettability,such as modified carbon fiber,surfactants,and aluminum alloys.展开更多
A novel three-dimension(3D)graphene/MgO composite was synthesized through self-assembly and embedding MgO nanoparticle in reduced graphene in situ.Fourier transform infrared(FT-IR)spectroscopy,thermal gravimetric anal...A novel three-dimension(3D)graphene/MgO composite was synthesized through self-assembly and embedding MgO nanoparticle in reduced graphene in situ.Fourier transform infrared(FT-IR)spectroscopy,thermal gravimetric analysis(TGA),scanning electron microscopy(SEM),transmission electron microscope(TEM),powder X-raydiffraction(XRD)and X-rayphotoelectron spectroscopy(XPS)were employed to characterize the prepared 3D graphene/MgO composite.The adsorption performance of some metal ions on 3D graphene/MgO was investigated.The results showed that the adsorption capacity was greater than 3D graphene and the maximum adsorption capacity at 25℃was found to be 358.96 mg/g,388.4 mg/g and 169.8 mg/g for Pb^2+,Cd^2+and Cu^2+,respectively.The adsorption kinetic conformed to the pseudo-second-order kinetic model and the adsorption isotherm was well described by Langmuir model.The thermodynamic constants revealed that the sorption process was endothermic and spontaneous in nature.Based on the results of the removal of heavy metal ions from metal smelting wastewater,it can be concluded that the prepared 3D graphene/MgO composite is an effective and potential adsorbent.展开更多
Three-dimensional(3 D)frameworks have received much attention as an effective modification strategy for next-generation high-energy-density lithium metal batteries.However,the top-growth mode of lithium(Li)on the 3 D ...Three-dimensional(3 D)frameworks have received much attention as an effective modification strategy for next-generation high-energy-density lithium metal batteries.However,the top-growth mode of lithium(Li)on the 3 D framework remains a tough challenge.To achieve a uniform bottom-up Li growth,a scheme involving Ag concentration gradient in 3 D PVDF framework(C-Ag/PVDF)is proposed.Ag nanoparticles with a concentration gradient induce an interface activity gradient in the 3 D framework,and this gradient feature is still maintained during the cycle.As a result,the C-Ag/PVDF framework delivers a long lifespan over 1800 h at a current density of 1 mA cm^(-2) with a capacity of 1 mAh cm^(-2),and shows an ultra-long life(>1300 h)even at a high current density of 4 mA cm^(-2) with a capacity of 4 mAh cm^(-2).The advantage of concentration gradient provides further insights into the optimal design of the 3 D framework for stable Li metal anode.展开更多
Lithium(Li)metal is regarded as one of the most promising anode candidates for next-generation batteries due to its extremely high specific capacity and low redox potential.However,its application is still hindered by...Lithium(Li)metal is regarded as one of the most promising anode candidates for next-generation batteries due to its extremely high specific capacity and low redox potential.However,its application is still hindered by the uncontrolled growth of dendritic Li and huge volume fluctuation during cycles.To address these issues,flexible and self-supporting three-dimensional(3D)interlaced Ndoped carbon nanofibers(NCNFs)coated with uniformly distributed 2D ultrathin NiCo_(2)S_(4)nanosheets(denoted CNCS)were designed to eliminate the intrinsic hotspots for Li deposition.Physicochemical dual effects of CNCS arise from limited surface Li diffusivity with a higher Li affinity,leading to uniform Li nucleation and less random accumulation of Li,as confirmed by ab initio molecular dynamics simulations.Due to the unique structure,exchange current density is reduced significantly and metallic Li is further contained within the interspace between the NCNF and NiCo_(2)S_(4)nanosheets,preventing the formation of dendritic Li.The symmetric cell with a Li/CNCS composite anode shows a long-running lifespan for almost 1200 h,with an exceptionally low and stable overpotential under 1mA cm^(-2)/1 mAh cm^(-2).A full cell coupled with a LiFePO4 cathode at a low N/P ratio of 2.45 shows typical voltage profiles but more significantly enhanced performance than that of a LiFePO4 cathode coupled with a bare Li anode.展开更多
Lithium(Li)metal is the most potential anode material for the next-generation high-energy rechargeable batteries.However,intrinsic surface unevenness and‘hostless’nature of Li metal induces infinite volume effect an...Lithium(Li)metal is the most potential anode material for the next-generation high-energy rechargeable batteries.However,intrinsic surface unevenness and‘hostless’nature of Li metal induces infinite volume effect and uncontrollable dendrite growth.Herein,we design the in-situ grown lithiophilic Ni_(2)P nanoarrays inside nickel foam(PNF).Uniform Ni_(2)P nanoarrays coating presents a very low nucleation overpotential,which induces the homogeneous Li deposition in the entire spaces of three-dimensional(3D)metal framework.Specifically,the lithiophilic Ni_(2)P nanoarrays possess characteristics of electrical conductivity and structural stability,which have almost no expansion and damage during repeating Li plating/stripping.Therefore,they chronically inhibit the growth of Li dendrites.This results in an outstanding Coulombic efficiency(CE)of 98% at 3 mA cm^(-2) and an ultra long cycling life over 2000 cycles with a low overpotential.Consequently,the PNF-Li||LiFePO_(4) battery maintains a capacity retention of 95.3% with a stable CE of 99.9% over 500 cycles at 2 C.展开更多
Lithium metal anode has been demonstrated as the most promising anode for lithium batteries because of its high theoretical capacity,but infinite volume change and dendritic growth during Li electrodeposition have pre...Lithium metal anode has been demonstrated as the most promising anode for lithium batteries because of its high theoretical capacity,but infinite volume change and dendritic growth during Li electrodeposition have prevented its practical applications.Both physical morphology confinement and chemical adsorption/diffusion regulation are two crucial approaches to designing lithiophilic materials to alleviate dendrite of Li metal anode.However,their roles in suppressing dendrite growth for long-life Li anode are not fully understood yet.Herein,three different Ni-based nanosheet arrays(NiO-NS,Ni_(3)N-NS,and Ni_(5)P_(4)-NS)on carbon cloth as proof-of-concept lithiophilic frame-works are proposed for Li metal anodes.The two-dimensional nanoarray is more promising to facilitate uniform Li^(+)flow and electric field.Compared with the NiO-NS and the Ni_(5)P_(4)-NS,the Ni_(3)N-NS on carbon cloth after reacting with molten Li(Li-Ni/Li_(3)N-NS@CC)can afford the strongest adsorption to Li+and the most rapid Li+diffusion path.Therefore,the Li-Ni/Li_(3)N-NS@CC electrode realizes the lowest overpotential and the most excellent electrochemical performance(60 mA cm^(−2)and 60 mAh cm^(−2)for 1000 h).Furthermore,a remarkable full battery(LiFePO_(4)||Li-Ni/Li_(3)N-NS@CC)reaches 300 cycles at 2C.This research provides valuable insight into designing dendrite-free alkali metal batteries.展开更多
Lithium metal anode holds an important position in fast-charging batteries.But lithium dendrite issues tend to exacerbate at high currents.Li F can be considered as an effective way to improve the Li metal surface ele...Lithium metal anode holds an important position in fast-charging batteries.But lithium dendrite issues tend to exacerbate at high currents.Li F can be considered as an effective way to improve the Li metal surface electrochemical stability to achieve high power and high energy.However,most of reported work are relying on in situ formation of a 2D Li F on Li metal in liquid electrolyte,which limits the scalability and plated Li quantity.Here,we address this challenge and report a scalable synthesis of Li F-rich 3D architected Li metal anode via a direct pyrolysis of molten lithium and fluoropolymer to enable fast Li charging with high current density(20 mA cm-2)and high areal capacity(20 m Ah cm-2).The 3D structure is synthesized by the pyrolysis of fluoropolymer with Li metal and results show high similarity to the pristine electrolyte-derived solid-electrolyte-interphase(SEI).This concept using pyrolysis of fluoropolymer with Li-containing active materials could be also extended to modify Li metal oxide cathode(e.g.,Li Ni0.5Mn1.5O4)for mixed conductive interphase and engineer Li solid ion conductors(e.g.,Li garnet-type oxides)for interface stabilization andframework design.展开更多
Recently, two dimensional In Se attracts great attentions as potential hydrogen production photocatalysts.Here, comprehensive investigations on the hydrogen evolution reaction activity of In Se monolayer with3 d trans...Recently, two dimensional In Se attracts great attentions as potential hydrogen production photocatalysts.Here, comprehensive investigations on the hydrogen evolution reaction activity of In Se monolayer with3 d transition metal doping and biaxial strain were performed based on the density functional theory.Transition metal dopants significantly increase the bonding strength between H and Se, and then adjust the hydrogen adsorption free energy to 0.02 e V by Zn doping. The enhanced hydrogen evolution reaction activity results from less electron occupying H 1 s-Se 4 pzanti-bonding states, which is well correlated with the pzband center level. Importantly, the universal scalling law was proposed to descript the evolution of hydrogen adsorption free energy including both doping and strain effects. Moreover, with appropriate band alignment, optical absorption, and carriers separation ability, Zn doped In Se monolayer is considered as a promising candidate of visible-light photocatalyst for hydrogen production.展开更多
基金supported by the Shanghai Agricultural Science and Technology Program (2022-02-08-00-12-F01176)he National Natural Science Foundation of China (52006135)
文摘Direct air capture(DAC)of CO_(2)plays an indispensable role in achieving carbon-neutral goals as one of the key negative emission technologies.Since large air flows are required to capture the ultradilute CO_(2)from the air,lab-synthesized adsorbents in powder form may cause unacceptable gas pressure drops and poor heat and mass transfer efficiencies.A structured adsorbent is essential for the implementation of gas-solid contactors for cost-and energy-efficient DAC systems.In this study,efficient adsorbent poly(ethyleneimine)(PEI)-functionalized Mg-Al-CO_(3)layered double hydroxide(LDH)-derived mixed metal oxides(MMOs)are three-dimensional(3D)printed into monoliths for the first time with more than 90%adsorbent loadings.The printing process has been optimized by initially printing the LDH powder into monoliths followed by calcination into MMO monoliths.This structure exhibits a 32.7%higher specific surface area and a 46.1%higher pore volume,as compared to the direct printing of the MMO powder into a monolith.After impregnation of PEI,the monolith demonstrates a large adsorption capacity(1.82 mmol/g)and fast kinetics(0.7 mmol/g/h)using a CO_(2)feed gas at 400 ppm at 25℃,one of the highest values among the shaped DAC adsorbents.Smearing of the amino-polymers during the post-printing process affects the diffusion of CO_(2),resulting in slower adsorption kinetics of pre-impregnation monoliths compared to post-impregnation monoliths.The optimal PEI/MeOH ratio for the post-impregnation solution prevents pores clogging that would affect both adsorption capacity and kinetics.
基金This work was financially supported by Stable Support Plan Program for Higher Education Institutions(20220815094504001)Shenzhen Key Laboratory of Advanced Energy Storage(ZDSYS20220401141000001)+1 种基金This work was also financially supported by the Shenzhen Science and Technology Innovation Commission(GJHZ20200731095606021,20200925155544005)the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone(HZQB-KCZYB-2020083)。
文摘Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport.Solid electrolytes are generally studied as two-dimensional(2D)structures with planar interfaces,showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces.Herein,three-dimensional(3D)architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment.Multiple-type electrolyte films with vertical-aligned micro-pillar(p-3DSE)and spiral(s-3DSE)structures are rationally designed and developed,which can be employed for both Li metal anode and cathode in terms of accelerating the Li+transport within electrodes and reinforcing the interfacial adhesion.The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm^(−2).The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm^(−2)(LFP)and 3.92 mAh cm^(−2)(NCM811).This unique design provides enhancements for both anode and cathode electrodes,thereby alleviating interfacial degradation induced by dendrite growth and contact loss.The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.
基金supported by National Natural Science Foundation of China(21701083).
文摘At present,commercial Li-ion batteries are hardly to satisfy the growing demand for high energy density,for this purpose,lithium metal batteries have attracted worldwide attention in recent years.However,its practical applications are hindered by the formation of Li dendrites and volume effect during Li plating/stripping process,which leads to a lot of safety hazards.Herein,we first employed MOF-derived V_(2)O_(5) nanoparticles to decorate the carbon fiber cloth(CFC)backbone to acquire a lithiophilic 3D porous conductive framework(CFC@V_(2)O_(5)).Subsequently,the CFC@V_(2)O_(5) skeleton was permeated with molten Li to prepare CFC@V_(2)O_(5)@Li composite anode.The CFC@V_(2)O_(5)@Li composite anode can be stably cycled for more than 1650 h at high current density(5 mA·cm^(-2))and areal capacity(5 mA·h·cm^(–2)).The prepared full cell can initially maintain a high capacity of about 143 mA·h·g^(-1) even at a high current density of 5 C,and can still maintain 114 mA·h·g^(-1) after 1000 cycles.
基金financially the National Natural Science Foundation of China(Nos.22178221,22208221)Shenzhen Science and Technology Program(Nos.JCYJ20200109105805902)+1 种基金Natural Science Foundation of Guangdong Province(Nos.2021A1515110751)China Postdoctoral Science Foundation(Nos.2021M702255)。
文摘The ripple effect induced by uncontrollable Zn deposition is considered as the Achilles heel for developing high-performance aqueous Zn-ion batteries.For this problem,this work reports a design concept of 3D artificial array interface engineering to achieve volume stress elimination,preferred orientation growth and dendrite-free stable Zn metal anode.The mechanism of MXene array interface on modulating the growth kinetics and deposition behavior of Zn atoms were firstly disclosed on the multi-scale level,including the in-situ optical microscopy and transient simulation at the mesoscopic scale,in-situ Raman spectroscopy and in-situ X-ray diffraction at the microscopic scale,as well as density functional theory calculation at the atomic scale.As indicated by the electrochemical performance tests,such engineered electrode exhibits the comprehensive enhancements not only in the resistance of corrosion and hydrogen evolution,but also the rate capability and cyclic stability.High-rate performance(20 mA cm^(-2))and durable cycle lifespan(1350 h at 0.5 mA cm^(-2),1500 h at 1 mA cm^(-2)and 800 h at 5 mA cm^(-2))can be realized.Moreover,the improvement of rate capability(214.1 mAh g^(-1)obtained at 10 A g^(-1))and cyclic stability also can be demonstrated in the case of 3D MXene array@Zn/VO2battery.Beyond the previous 2D closed interface engineering,this research offers a unique 3D open array interface engineering to stabilize Zn metal anode,the controllable Zn deposition mechanism revealed is also expected to deepen the fundamental of rechargeable batteries including but not limited to aqueous Zn metal batteries.
基金supported through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(2022M3H4A1A04096478)the support from the Supercomputing Center of Wuhan University。
文摘Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline HER kinetics.Here,we design ternary transition metals-based nickel telluride(Mo WNi Te)catalysts consisting of high valence non-3d Mo and W metals and oxophilic Te as a first demonstration of non-precious heterogeneous electrocatalysts following the bifunctional mechanism.The Mo WNi Te showed excellent HER catalytic performance with overpotentials of 72,125,and 182 mV to reach the current densities of 10,100,and 1000 mA cm^(-2),respectively,and the corresponding Tafel slope of 47,52,and 58 mV dec-1in alkaline media,which is much superior to commercial Pt/C.Additionally,the HER performance of Mo WNi Te is well maintained up to 3000 h at the current density of 100 mA cm^(-2).It is further demonstrated that the Mo WNi Te exhibits remarkable HER activities with an overpotential of 45 mV(31 mV)and Tafel slope of 60 mV dec-1(34 mV dec-1)at 10 mA cm^(-2)in neutral(acid)media.The superior HER performance of Mo WNi Te is attributed to the electronic structure modulation,inducing highly active low valence states by the incorporation of high valence non-3d transition metals.It is also attributed to the oxophilic effect of Te,accelerating water dissociation kinetics through a bifunctional catalytic mechanism in alkaline media.Density functional theory calculations further reveal that such synergistic effects lead to reduced free energy for an efficient water dissociation process,resulting in remarkable HER catalytic performances within universal pH environments.
基金financial support of this research by the National Natural Science Foundation of China (No. 51905446)the Research Center for Industries of the Future (RCIF) at Westlake University for partially supporting this work。
文摘Three-dimensional-structured metal oxides have myriad applications for optoelectronic devices.Comparing to conventional lithography-based manufacturing methods which face significant challenges for 3D device architectures,additive manufacturing approaches such as direct ink writing offer convenient,on-demand manufacturing of 3D oxides with high resolutions down to sub-micrometer scales.However,the lack of a universal ink design strategy greatly limits the choices of printable oxides.Here,a universal,facile synthetic strategy is developed for direct ink writable polymer precursor inks based on metal-polymer coordination effect.Specifically,polyethyleneimine functionalized by ethylenediaminetetraacetic acid is employed as the polymer matrix for adsorbing targeted metal ions.Next,glucose is introduced as a crosslinker for endowing the polymer precursor inks with a thermosetting property required for 3D printing via the Maillard reaction.For demonstrations,binary(i.e.,ZnO,CuO,In_(2)O_(3),Ga_(2)O_(3),TiO_(2),and Y_(2)O_(3)) and ternary metal oxides(i.e.,BaTiO_(3) and SrTiO_(3)) are printed into 3D architectures with sub-micrometer resolution by extruding the inks through ultrafine nozzles.Upon thermal crosslinking and pyrolysis,the 3D microarchitectures with woodpile geometries exhibit strong light-matter coupling in the mid-infrared region.The design strategy for printable inks opens a new pathway toward 3D-printed optoelectronic devices based on functional oxides.
基金supported by the National Research Council of Science & Technology (NST) grant by the Korea Government (MSIT) (grant no.CRC23011-000)by the National Research Foundation of Korea (NRF) funded by the Ministry of Science,ICT,and Future Planning (MSIP,South Korea) (grant no.NRF-2021R1C1C1007645)。
文摘This study presents a novel process for the fabrication of metal-intermetallic composites with a 3D bicontinuous structure, achieved through a combination of liquid metal dealloying(LMD) and subsequent alloying. Initially, porous Ti structures are produced using the LMD process, followed by immersion in a molten Mg-3Al(wt%) metal. Due to the higher thermodynamic miscibility of Al with Ti compared to Mg, the concentration of Al in the Ti matrix increases as the immersion time increases. This results in a sequential phase transition within the Ti matrix: α-Ti → Ti_(3)Al → Ti Al. The phase transition considerably affects the hardness and strength of the composite material,with the Mg-Ti_(3)Al-Ti Al composite exhibiting a maximum hardness nearly twice as high as that of the conventional Mg-Ti composite. This innovative process holds potential for the development of various bicontinuous metal-intermetallic composites.
基金supported by the Chinese National Natural Science Foundation(No.22075008,21571010,U0734002)National Basic Research Programs of China(973 Program,No.2014CB931800,2011CB935700)+1 种基金Chinese Aeronautic Project(No.2013ZF51069)111 Project(No.B14009).
文摘Li metal with high-energy density is considered as the most promising anode for the next-generation rechargeable Li metal batteries;however,the growth of Li dendrites seriously hinders its practical application.Herein,3D free-standing carbon nanofibers modified by lithiophilic metal particles(CNF/Me,Me=Sn,Fe,Co)are obtained in situ by the electrospinning method.Benefiting from the lithophilicity,the CNF/Me composite may effectively prevent the formation of Li dendrites in the Li metal batteries.The optimized CNF/Sn–Li composite electrode exhibits a stable cycle life of over 2350 h during Li plating/stripping.When matched with typical commercial LiFePO_(4)(LFP)cathode,the LFP//CNF/Sn–Li full cell presents a high initial discharge specific capacity of 139 mAh g^(−1)at 1 C,which remains at 146 mAh g^(−1)after 400 cycles.When another state-of-the-art commercial LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM(811))cathode is used,the assembled NCM//CNF/Sn–Li full cell shows a large initial specific discharge capacity of 206 mAh g^(−1)at substantially enhanced 10 C,which keeps at the good capacity of 99 mAh g^(−1)after 300 cycles.These results are greatly superior to the counterparts with Li as the anodes,indicating the great potential for practical utilization of the advanced CNF/Sn–Li electrode.
基金supported by the National Institute of Arthritis and Musculoskeletal and Skin Diseases of the National Institutes of Health under Award Number R01 AR067306-01 and R01 AR078241(PI—Bandyopadhyay)。
文摘Porous and functionally graded materials have seen extensive applications in modern biomedical devices—allowing for improved site-specific performance;their appreciable mechanical,corrosive,and biocompatible properties are highly sought after for lightweight and high-strength load-bearing orthopedic and dental implants.Examples of such porous materials are metals,ceramics,and polymers.Although,easy to manufacture and lightweight,porous polymers do not inherently exhibit the required mechanical strength for hard tissue repair or replacement.Alternatively,porous ceramics are brittle and do not possess the required fatigue resistance.On the other hand,porous biocompatible metals have shown tailorable strength,fatigue resistance,and toughness.Thereby,a significant interest in investigating the manufacturing challenges of porous metals has taken place in recent years.Past research has shown that once the advantages of porous metallic structures in the orthopedic implant industry have been realized,their biological and biomechanical compatibility—with the host bone—has been followed up with extensive methodical research.Various manufacturing methods for porous or functionally graded metals are discussed and compared in this review,specifically,how the manufacturing process influences microstructure,graded composition,porosity,biocompatibility,and mechanical properties.Most of the studies discussed in this review are related to porous structures for bone implant applications;however,the understanding of these investigations may also be extended to other devices beyond the biomedical field.
基金supported by the National Natural Science Foundation of China(Grant No.51901082)the National Postdoctoral Program for Innovative Talents(BX20200137)the National Defense Basic Scientific Research Program of China(JCKY2018110C060)。
文摘Additive manufacturing(AM)is a free-form technology that shows great potential in the integrated creation of three-dimensional(3D)electronics.However,the fabrication of 3D conformal circuits that fulfill the requirements of high service temperature,high conductivity and high resolution remains a challenge.In this paper,a hybrid AM method combining the fused deposition modeling(FDM)and hydrophobic treatment assisted laser activation metallization(LAM)was proposed for manufacturing the polyetheretherketone(PEEK)-based 3D electronics,by which the conformal copper patterns were deposited on the 3D-printed PEEK parts,and the adhesion between them reached the 5B high level.Moreover,the 3D components could support the thermal cycling test from-55℃ to 125℃ for more than 100 cycles.Particularly,the application of a hydrophobic coating on the FDM-printed PEEK before LAM can promote an ideal catalytic selectivity on its surface,not affected by the inevitable printing borders and pores in the FDM-printed parts,then making the resolution of the electroless plated copper lines improved significantly.In consequence,Cu lines with width and spacing of only60μm and 100μm were obtained on both as-printed and after-polished PEEK substrates.Finally,the potential of this technique to fabricate 3D conformal electronics was demonstrated.
基金supported by the Technology Development Program(P0011350)funded by the Ministry of SMEs and Startups(MSS,Korea)。
文摘The use of commercial products such as a cup and liner for total hip arthroplasty for patients with severe bone defects has a high probability of failure.In these patients the cup alone cannot cover the bone defect,and thus,an additional augment or cage is required.In this study,we designed three-dimensional(3D)printable bone augments as an alternative to surgeries using reinforcement cages.Thirty-five sharp-edged bone augments of various sizes were 3D printed.A biporous structure was designed to reduce the weight of the augment and to facilitate bone ingrowth.Two types of frames were used to prevent damage to the augment’s porous structure and maintain its stability during printing.Furthermore,two types of holes were provided for easy augment fixation at various angles.Fatigue tests were performed on a combination of worst-case sizes derived using finite element analysis.The test results confirmed the structural stability of the specimens at a load of 5340 N.Although the porosity of the specimens was measured to be 63.70%,it cannot be said that the porous nature was uniformly distributed because porosity tests were performed locally and randomly.In summary,3D-printable biporous bone augments capable of bonding from various angles and bidirectionally through angulation and bottom-plane screw holes are proposed.The mechanical results with bone augments indicate good structural safety in patients.However,further research is necessary to study the clinical applications of the proposed bone augment.
基金Key R&D and transformation projects in Hebei Province,Grant/Award Number:21314401DProgram for the Development of Science and Technology of Jilin province,Grant/Award Numbers:20200201187JC,20200201277JC,20200201279JC+4 种基金Project of Development and Reform Commission of Jilin Province,Grant/Award Number:2020C026-3National Natural Science Foundation of China,Grant/Award Numbers:21978110,51772126,52171210Fundamental Research Funds for the Central Universities,Grant/Award Number:2021JCCXJD01Key R&D and transformation projects in Qinghai Province,Grant/Award Number:2021-HZ-808The talents project of Beijing Municipal Committee Organization Department,Grant/Award Number:2018000021223ZK21。
文摘Rational design of porous conductive hosts with high electrical conductivity,large surface area,and adequate interior space is desirable to suppressing dendritic lithium growth and accommodating large volume change of lithium metal anode during the Li plating/stripping process.However,due to the conductive nature of the conductive hosts,Li is easily deposited directly on the top of the hosts,which hinders it from fully functioning.To circumvent the issue,in this study,we designed a novel porous carbon host with a gradient-pore-size structure based on one-dimensional(1D)carbon with different diameters.With this kind of host,stable cycling with high and stable Coulombic efficiency of~98%is achieved at 0.5 mA cm^(−2) with an areal capacity of 1 mAh cm^(−2) over 320 cycles.In contrast,the normal three-dimensional(3D)carbon nanotube host presents a moss-like Li morphology with wildly fluctuating Coulombic efficiency after 100 cycles.The results reveal that the unique gradient-pore-size structure of the 3D conductive host greatly improves the performance of lithium metal batteries.
基金Supported by National Key R&D Program of China(Grant Nos.2017YFB1103400,2016YFB1100902)National Natural Science Foundation of China(Grant No.51575430,51811530107)The Youth Innovation Team of Shaanxi Universities.
文摘A novel metal matrix composite freeform fabrication approach,fiber traction printing(FTP),is demonstrated through controlling the wetting behavior between fibers and the matrix.This process utilizes the fiber bundle to control the cross-sectional shape of the liquid metal,shaping it from circular to rectangular which is more precise.The FTP process could resolve manufacturing difficulties in the complex structure of continuous fiber reinforced metal matrix composites.The printing of the first layer monofilament is discussed in detail,and the effects of the fibrous coating thickness on the mechanical properties and microstructures of the composite are also investigated in this paper.The composite material prepared by the FTP process has a tensile strength of 235.2 MPa,which is close to that of composites fabricated by conventional processes.The complex structures are printed to demonstrate the advantages and innovations of this approach.Moreover,the FTP method is suited to other material systems with good wettability,such as modified carbon fiber,surfactants,and aluminum alloys.
基金Projects(21571191,51674292) supported by the National Natural Science Foundation of ChinaProject(2016JJ1023) supported by the Natural Science Foundation of Hunan Province,ChinaProject(2018TP1003) supported by the Key Laboratory of Hunan Province for Water Environment and Agriculture Product Safety,China
文摘A novel three-dimension(3D)graphene/MgO composite was synthesized through self-assembly and embedding MgO nanoparticle in reduced graphene in situ.Fourier transform infrared(FT-IR)spectroscopy,thermal gravimetric analysis(TGA),scanning electron microscopy(SEM),transmission electron microscope(TEM),powder X-raydiffraction(XRD)and X-rayphotoelectron spectroscopy(XPS)were employed to characterize the prepared 3D graphene/MgO composite.The adsorption performance of some metal ions on 3D graphene/MgO was investigated.The results showed that the adsorption capacity was greater than 3D graphene and the maximum adsorption capacity at 25℃was found to be 358.96 mg/g,388.4 mg/g and 169.8 mg/g for Pb^2+,Cd^2+and Cu^2+,respectively.The adsorption kinetic conformed to the pseudo-second-order kinetic model and the adsorption isotherm was well described by Langmuir model.The thermodynamic constants revealed that the sorption process was endothermic and spontaneous in nature.Based on the results of the removal of heavy metal ions from metal smelting wastewater,it can be concluded that the prepared 3D graphene/MgO composite is an effective and potential adsorbent.
基金supported by the Fundamental Research Funds for the Central Universities,China(ZYGX2019Z008)the National Natural Science Foundation of China(52072061)the Open Fund of the Key Laboratory for Renewable Energy,Chinese Academy of Sciences,Beijing Key Laboratory for New Energy Materials and Devices。
文摘Three-dimensional(3 D)frameworks have received much attention as an effective modification strategy for next-generation high-energy-density lithium metal batteries.However,the top-growth mode of lithium(Li)on the 3 D framework remains a tough challenge.To achieve a uniform bottom-up Li growth,a scheme involving Ag concentration gradient in 3 D PVDF framework(C-Ag/PVDF)is proposed.Ag nanoparticles with a concentration gradient induce an interface activity gradient in the 3 D framework,and this gradient feature is still maintained during the cycle.As a result,the C-Ag/PVDF framework delivers a long lifespan over 1800 h at a current density of 1 mA cm^(-2) with a capacity of 1 mAh cm^(-2),and shows an ultra-long life(>1300 h)even at a high current density of 4 mA cm^(-2) with a capacity of 4 mAh cm^(-2).The advantage of concentration gradient provides further insights into the optimal design of the 3 D framework for stable Li metal anode.
基金Natural Sciences and Engineering Research Council of Canada,Grant/Award Numbers:Alliance‐Alberta Innovates Program/ALLRP‐561137‐20,Discovery Grant Program/RGPIN‐2020‐05184University of Alberta Future Energy Systems。
文摘Lithium(Li)metal is regarded as one of the most promising anode candidates for next-generation batteries due to its extremely high specific capacity and low redox potential.However,its application is still hindered by the uncontrolled growth of dendritic Li and huge volume fluctuation during cycles.To address these issues,flexible and self-supporting three-dimensional(3D)interlaced Ndoped carbon nanofibers(NCNFs)coated with uniformly distributed 2D ultrathin NiCo_(2)S_(4)nanosheets(denoted CNCS)were designed to eliminate the intrinsic hotspots for Li deposition.Physicochemical dual effects of CNCS arise from limited surface Li diffusivity with a higher Li affinity,leading to uniform Li nucleation and less random accumulation of Li,as confirmed by ab initio molecular dynamics simulations.Due to the unique structure,exchange current density is reduced significantly and metallic Li is further contained within the interspace between the NCNF and NiCo_(2)S_(4)nanosheets,preventing the formation of dendritic Li.The symmetric cell with a Li/CNCS composite anode shows a long-running lifespan for almost 1200 h,with an exceptionally low and stable overpotential under 1mA cm^(-2)/1 mAh cm^(-2).A full cell coupled with a LiFePO4 cathode at a low N/P ratio of 2.45 shows typical voltage profiles but more significantly enhanced performance than that of a LiFePO4 cathode coupled with a bare Li anode.
基金financial supported by the National Natural Science Foundation of China(Grant Nos.51874361 and 51904343)the Science and technology program of Hunan Province(2019RS3002)。
文摘Lithium(Li)metal is the most potential anode material for the next-generation high-energy rechargeable batteries.However,intrinsic surface unevenness and‘hostless’nature of Li metal induces infinite volume effect and uncontrollable dendrite growth.Herein,we design the in-situ grown lithiophilic Ni_(2)P nanoarrays inside nickel foam(PNF).Uniform Ni_(2)P nanoarrays coating presents a very low nucleation overpotential,which induces the homogeneous Li deposition in the entire spaces of three-dimensional(3D)metal framework.Specifically,the lithiophilic Ni_(2)P nanoarrays possess characteristics of electrical conductivity and structural stability,which have almost no expansion and damage during repeating Li plating/stripping.Therefore,they chronically inhibit the growth of Li dendrites.This results in an outstanding Coulombic efficiency(CE)of 98% at 3 mA cm^(-2) and an ultra long cycling life over 2000 cycles with a low overpotential.Consequently,the PNF-Li||LiFePO_(4) battery maintains a capacity retention of 95.3% with a stable CE of 99.9% over 500 cycles at 2 C.
基金supported by the National Key R&D Research Program of China the National Key Research Program(No.2018YFB0905400)the National Natural Science Foundation of China(Nos.51925207,U1910210,51872277,52002083,52102322 and 22109011)+5 种基金National Synchrotron Radiation Laboratory(KY2060000173)the“Transformational Technologies for Clean Energy and Demonstration”Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDA21000000)the Fundamental Research Funds for the Central Universities(Wk2060140026,Wk2400000004,Wk20720220010)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(Grant.YLU-DNL Fund 2021002)the National Postdoctoral Program for Innovative Talents(BX20200047)the China Postdoctoral Science Foundation(2021M690380).
文摘Lithium metal anode has been demonstrated as the most promising anode for lithium batteries because of its high theoretical capacity,but infinite volume change and dendritic growth during Li electrodeposition have prevented its practical applications.Both physical morphology confinement and chemical adsorption/diffusion regulation are two crucial approaches to designing lithiophilic materials to alleviate dendrite of Li metal anode.However,their roles in suppressing dendrite growth for long-life Li anode are not fully understood yet.Herein,three different Ni-based nanosheet arrays(NiO-NS,Ni_(3)N-NS,and Ni_(5)P_(4)-NS)on carbon cloth as proof-of-concept lithiophilic frame-works are proposed for Li metal anodes.The two-dimensional nanoarray is more promising to facilitate uniform Li^(+)flow and electric field.Compared with the NiO-NS and the Ni_(5)P_(4)-NS,the Ni_(3)N-NS on carbon cloth after reacting with molten Li(Li-Ni/Li_(3)N-NS@CC)can afford the strongest adsorption to Li+and the most rapid Li+diffusion path.Therefore,the Li-Ni/Li_(3)N-NS@CC electrode realizes the lowest overpotential and the most excellent electrochemical performance(60 mA cm^(−2)and 60 mAh cm^(−2)for 1000 h).Furthermore,a remarkable full battery(LiFePO_(4)||Li-Ni/Li_(3)N-NS@CC)reaches 300 cycles at 2C.This research provides valuable insight into designing dendrite-free alkali metal batteries.
基金supported by the startup funding at University of Delaware
文摘Lithium metal anode holds an important position in fast-charging batteries.But lithium dendrite issues tend to exacerbate at high currents.Li F can be considered as an effective way to improve the Li metal surface electrochemical stability to achieve high power and high energy.However,most of reported work are relying on in situ formation of a 2D Li F on Li metal in liquid electrolyte,which limits the scalability and plated Li quantity.Here,we address this challenge and report a scalable synthesis of Li F-rich 3D architected Li metal anode via a direct pyrolysis of molten lithium and fluoropolymer to enable fast Li charging with high current density(20 mA cm-2)and high areal capacity(20 m Ah cm-2).The 3D structure is synthesized by the pyrolysis of fluoropolymer with Li metal and results show high similarity to the pristine electrolyte-derived solid-electrolyte-interphase(SEI).This concept using pyrolysis of fluoropolymer with Li-containing active materials could be also extended to modify Li metal oxide cathode(e.g.,Li Ni0.5Mn1.5O4)for mixed conductive interphase and engineer Li solid ion conductors(e.g.,Li garnet-type oxides)for interface stabilization andframework design.
基金supported by the National Natural Science Foundation of China(11804023)the Natural Science Foundation of Tianjin(18JCQNJC02700)。
文摘Recently, two dimensional In Se attracts great attentions as potential hydrogen production photocatalysts.Here, comprehensive investigations on the hydrogen evolution reaction activity of In Se monolayer with3 d transition metal doping and biaxial strain were performed based on the density functional theory.Transition metal dopants significantly increase the bonding strength between H and Se, and then adjust the hydrogen adsorption free energy to 0.02 e V by Zn doping. The enhanced hydrogen evolution reaction activity results from less electron occupying H 1 s-Se 4 pzanti-bonding states, which is well correlated with the pzband center level. Importantly, the universal scalling law was proposed to descript the evolution of hydrogen adsorption free energy including both doping and strain effects. Moreover, with appropriate band alignment, optical absorption, and carriers separation ability, Zn doped In Se monolayer is considered as a promising candidate of visible-light photocatalyst for hydrogen production.