Compared to subtractive manufacturing and casting,3D printing(additive manufacturing)offers advantages,such as the rapid production of complex structures,reduced material waste,and environmental friendliness.Direct in...Compared to subtractive manufacturing and casting,3D printing(additive manufacturing)offers advantages,such as the rapid production of complex structures,reduced material waste,and environmental friendliness.Direct ink writing(DIW)is one of the most popular 3D printing techniques owing to its ability to print multiple materials simultaneously and its high compatibility with printing inks.However,DIW presents significant challenges,particularly in the printing of high-performance polymers.The main challenges are as follows:1.The rigid structures and reaction kinetics of high-performance polymers make developing new inks difficult.2.The limited types of available high-performance polymers underscore the need for new DIW-suitable materials.3.Layer-by-layer stacking weakens interlayer bonding,affecting the mechanical properties of the printed product.4.The accuracy and speed of DIW printing are insufficient for large-scale manufacturing.After introducing the topic,the requirements for DIW printing inks are first reviewed,emphasizing the importance of thixotropic agents.Then,research progress regarding DIW printing of high-performance polymers is comprehensively reviewed according to the requirements of different polymer inks.Additionally,the applications of these materials across various fields are summarized.Finally,the challenges in DIW printing of high-performance polymers,along with corresponding solutions and future development prospects,are discussed in detail.展开更多
Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation...Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation reaction.The structures of PIKs are characterized by means of elemental analysis,FT-IR,~1H-NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structure.The general properties of PIKs are studied by DSC,TG and wide-angle X-ray diffraction,the solubility behavior is...展开更多
Polymer solar cells(PSCs)consisting of a polymer donor and a small molecular acceptor is a promising photovoltaic technology,whose device performance is determined by both polymer donor and small molecular acceptor.Ha...Polymer solar cells(PSCs)consisting of a polymer donor and a small molecular acceptor is a promising photovoltaic technology,whose device performance is determined by both polymer donor and small molecular acceptor.Halogen atoms such as fluorine or chlorine atoms were usually introduced onto the polymer donors to downshift the highest occupied molecular orbital(HOMO)energy levels and improve the open-circuit voltage(VOC)of the PSCs.However,the introduction of the halogen atoms especially fluorine atoms greatly complicates the polymer synthesis.Herein,we report the use of a structural simple and easily synthesized building block,3,4-dicyanothiophene(DCT),to construct a set of halogen-free polymer donors PBCNTx(x=25,50,75)via ternary random copolymerization.The introduction of DCT units not only simplified the synthesis,but also downshifted the HOMO energy levels of the polymers and improved the V_(OC) of PSCs effectively.Encouragingly,the PBCNT75 afforded a power conversion efficiency up to 15.7%with a V_(OC) of 0.83 V,which are among the top values for halogen-free polymer donors.This work shows that the introduction of DCT units is a simple yet effective strategy to construct halogen-free and low-cost polymer donors for high-performance PSCs.展开更多
A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal st...A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.展开更多
The practical application of poly(ethylene oxide)(PEO)-based solid polymer electrolytes in all-solid-state lithium-metal batteries(ASSLBs)still suffers from persistent challenges associated with low ionic conductivity...The practical application of poly(ethylene oxide)(PEO)-based solid polymer electrolytes in all-solid-state lithium-metal batteries(ASSLBs)still suffers from persistent challenges associated with low ionic conductivity and poor oxidative stability.To address these issues,we introduce a novel in-situ ionization strategy using radical polymer poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl acrylate)(PTPA)to enhance ionic conductivity and achieve a high electrochemical stability window in PEO-based electrolyte.Density functional theory(DFT)calculations and molecular dynamics(MD)simulations reveal that the in-situ generation of PTPA+from PTPA within the battery,not only exceptionally decreases the low Highest Occupied Molecular Orbital(HOMO)energy level,but also exhibits a robust anchoring effect on TFSI-anions in the electrolyte,which boosts Li^(+) migration and enables dense Li deposition behavior.As a result,the PEO/10 wt%PTPA/LiTFSI electrolyte demonstrates remarkable oxidative stability up to 5 V and a high Li^(+)transference number(0.57).Li-Li symmetric cells maintain stability over 1000 h at 0.2 mA cm^(-2),and LiFePO_(4)(LFP)//Li battery also presents an enduring cyclic performance over 500 cycles with a remarkable high-capacity retention of 91.8% at 0.5C.Impressively,by coupling with a high-voltage LiCoO_(2)(LCO)cathode(cut-off voltage 4.6 V),the assembled ASSLBs reach a capacity retention of 87.1% after 500 cycles at 1C.Our study explores the mechanism of radical polymer in PEO-based electrolyte and provides a fire-new strategy for construction of high-performance and multifunctional ASSLBs.展开更多
Quasi-solid-state composite electrolytes(QSCEs)show promise for high-performance solid-state batteries,while they still struggle with interfacial stability and cycling performance.Herein,a F-grafted QSCE(F-QSCE)was de...Quasi-solid-state composite electrolytes(QSCEs)show promise for high-performance solid-state batteries,while they still struggle with interfacial stability and cycling performance.Herein,a F-grafted QSCE(F-QSCE)was developed via copolymerizing the F monomers and ionic liquid monomers.The F-QSCE demonstrates better overall performance,such as high ionic conductivity of 1.21 mS cm^(-1)at 25℃,wide electrochemical windows of 5.20 V,and stable cycling stability for Li//Li symmetric cells over 4000 h.This is attributed to the significant electronegativity difference between C and F in the fluorinated chain(-CF_(2)-CF-CF_(3)),which causes the electron cloud to shift toward the F atom,surrounding it with a negative charge and producing the inductive effect.Furthermore,the interactions between Li^(+)and F,TFSI~-,and C are enhanced,reducing ion pair aggregation(Li^(+)-TFSI~--Li^(+))and promoting Li^(+)transport.Besides,-CF_(2)-CF-CF_(3)decomposes to form Li F preferentially over TFSI~-,resulting in better interfacial stability for F-QSCE.This work provides a pathway to enable the development of high-performance Li metal batteries.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
CONSPECTUS:Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable,high-performance,polymeric materials.Although lignin is a highly available and low-cost source of natural aromatics,it is...CONSPECTUS:Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable,high-performance,polymeric materials.Although lignin is a highly available and low-cost source of natural aromatics,it is commonly burned for heat or disposed of as waste.The use of lignin for new materials introduces both challenges and opportunities with respect to incumbent petrochemical-based compounds.These considerations are derived from two fundamental aspects of lignin:its recalcitrant/heterogeneous nature and aromatic methoxy substituents.展开更多
Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode...Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode,low intrinsic conductivity of sulfur cathode,and severe shuttling effect of sodium polysulfides(NaPSs)pose significant challenges in the actual reversible capacity and cycle life of Na-S batteries.Herein,a self-supporting electrode made of nitrogen-doped carbon fiber embedded with cobalt nanoparticles(Co/NC-CF)is designed to load sulfur.Meanwhile,gel polymer electrolyte(GPE)with high ion transfer ability is obtained by in-situ polymerization inside the battery.During the polymerization process,an integrated electrode-electrolyte and a continuous ion-electron conduction network in a composite cathode are constructed inside the Na-S battery.It is noteworthy that the designed GPE demonstrates superior ionic conductivity and effective adsorption of NaPSs that can significantly suppress the shuttle effect.Leveraging the synergistic interplay between the designed GPE and self-supporting cathode,the assembled quasi-solid-state(QSS)Na-S battery exhibits great cycling stability.These experimental results are further corroborated by COMSOL Multiphysics simulations and density functional theory(DFT)calculations,which mechanistically validate the enhanced electrochemical performance.The findings of this study offer new and promising perspectives for advancing the development of nextgeneration solid-state batteries.展开更多
Solid-state polymer electrolytes are crucial for advancing solid-state lithium-metal batteries owing to their flexibility,excellent manufacturability,and strong interfacial compatibility.However,their widespread appli...Solid-state polymer electrolytes are crucial for advancing solid-state lithium-metal batteries owing to their flexibility,excellent manufacturability,and strong interfacial compatibility.However,their widespread applications are hindered by low ionic conductivity at room temperature and lithium dendrite growth.Herein,we report a novel solid-state composite membrane electrolyte design that combines the vertically aligned channel structure and copolymer with a radial gradient composition.Within the vertically aligned channels,the composition of poly(vinyl ethylene carbonate-co-poly(ethylene glycol)diacrylate)(P(VEC-PEGDA)varies in a gradient along the radial direction:from the center to the wall of vertically aligned channels,the proportion of vinyl ethylene carbonate(VEC)in the copolymer decreases,while the proportion of poly(ethylene glycol)diacrylate(PEGDA)increases accordingly.It can be functionally divided into a mechanical-reinforcement layer and a fast-ion-conducting layer.The resulting solid-state composite membrane electrolyte achieves a high critical current density of 1.2 mA cm^(-2)and high ionic conductivity of 2.03 mS cm^(-1)at room temperature.Employing this composite membrane electrolyte,a Li//Li symmetric cell exhibits stable cycling for over 1850 h at 0.2 m A cm^(-2)/0.2 m A h cm^(-2),and a Li//LiFePO4(LFP)battery maintains 77.3% capacity retention at 2 C after 300 cycles.Our work provides insight into the rational design of safer and more efficient solidstate batteries through electrolyte structural engineering.展开更多
This work focuses on the development of high temperature polymer electrolyte membranes(HT-PEMs)as key materials for HT-PEM fuel cells(HT-PEMFCs).Recognizing the challenges associated with the phosphoric acid(PA) doped...This work focuses on the development of high temperature polymer electrolyte membranes(HT-PEMs)as key materials for HT-PEM fuel cells(HT-PEMFCs).Recognizing the challenges associated with the phosphoric acid(PA) doped polybenzimidazole(PBI) membranes,including the use of carcinogenic monomers and complex synthesis procedures,this study aims to develop more cost-effective,readily synthesized,and high-performance alternatives.A series of superacid-catalyzed polyhydroxyalkylation reactions have been carefully designed between p-terphenyl and aldehydes bearing imidazole moieties,resulting in a new class of HT-PEMs.It is found that the chemical structure of aldehyde-substituted N-heterocycles significantly impacts the polymerization reaction.Specifically,the use of 1-methyl-2-imidazole-formaldehyde and 1 H-imidazole-4-formaldehyde monomers leads to the formation of high-viscosity,rigid,and ether-free polymers,denoted as PTIm-a and PTIm-b.Membranes fabricated from these polymers,due to their pendent imidazole groups,exhibit an exceptional capacity for PA absorption.Notably,PTIm-a,carrying methylimidazole moieties,demonstrates a superior chemical stability by maintaining morphology and structural stability during 350 h of Fenton testing.After being immersed in 75 wt% PA at 40℃,the PTIm-a membrane reaches a PA content of 152%,maintains a good tensile strength of 13.6 MPa,and exhibits a moderate conductivity of 50.2 mS cm^(-1) at 180℃.Under H_(2)/O_(2) operational conditions,a single cell based on the PTIm-a membrane attains a peak power density of 732 mW cm^(-2) at 180℃ without backpressure.Furthermore,the membrane demonstrates stable cycle stability over 173 h within 18 days at a current density of 200 mA cm^(-2),indicating its potential for practical application in HT-PEMFCs.This work highlights innovative strategies for the synthesis of advanced HT-PEMs,offering significant improvements in membrane properties and fuel cell performance,thus expanding the horizons of HT-PEMFC technology.展开更多
To address the issues in aqueous zinc-ion batteries(ZIBs),including the formation of zinc dendrites and the occurrence of harmful side reactions(e.g.,the hydrogen evolution reaction),which seriously affect the perform...To address the issues in aqueous zinc-ion batteries(ZIBs),including the formation of zinc dendrites and the occurrence of harmful side reactions(e.g.,the hydrogen evolution reaction),which seriously affect the performance of the battery,a sulfonated covalent organic framework(SCOF),TpPa-SO3H,was synthesized and the quasi-solid polymer electrolyte SCOF-PVDF/Zn(CF3SO3)2 was successfully prepared with a polymer matrix of PVDF and an ion-transporting backbone of SCOF.Both of Zn//Zn symmetric batteries and Zn//NH4V4O10 full batteries assembled using SCOF-PVDF/Zn(CF3SO3)2 electrolyte exhibited excellent battery cycling stability.The high ionic conductivity of 3×10^(-4)S·cm^(-1)could be achieved.The assembled symmetric batteries demonstrated a cycle life of 980 h at a current density of 2 mA·cm^(-2).The Zn//NH4V4O10 full battery can provide a specific capacity of 196 mAh·g^(-1)at a high current density of 10 A·g^(-1).展开更多
In the pursuit of ultrathin polymer electrolyte(<20 μm) for lithium metal batteries, achieving a balance between mechanical strength and interfacial stability is crucial for the longevity of the electrolytes.Herei...In the pursuit of ultrathin polymer electrolyte(<20 μm) for lithium metal batteries, achieving a balance between mechanical strength and interfacial stability is crucial for the longevity of the electrolytes.Herein, 11 μm-thick gel polymer electrolyte is designed via an integrated electrode/electrolyte structure supported by lithium metal anode. Benefiting from an exemplary superiority of excellent mechanical property, high ionic conductivity, and robust interfacial adhesion, the in-situ formed polymer electrolyte reinforced by titanosiloxane networks(ISPTS) embodies multifunctional roles of physical barrier, ionic carrier, and artificial protective layer at the interface. The potent interfacial interactions foster a seamless fusion of the electrode/electrolyte interfaces and enable continuous ion transport. Moreover, the built-in ISPTS electrolyte participates in the formation of gradient solid-electrolyte interphase(SEI) layer, which enhances the SEI's structural integrity against the strain induced by volume fluctuations of lithium anode.Consequently, the resultant 11 μm-thick ISPTS electrolyte enables lithium symmetric cells with cycling stability over 600 h and LiFePO_(4) cells with remarkable capacity retention of 96.6% after 800 cycles.This study provides a new avenue for designing ultrathin polymer electrolytes towards stable, safe,and high-energy–density lithium metal batteries.展开更多
The continuously growing importance of batteries for powering(hybrid)electric vehicles and storing renewable energy has prompted a renewed focus on lithium-metal batteries(LMBs)in recent years,as its high theoretical ...The continuously growing importance of batteries for powering(hybrid)electric vehicles and storing renewable energy has prompted a renewed focus on lithium-metal batteries(LMBs)in recent years,as its high theoretical specific capacity of about 3860 mA h g^(-1) and very low redox potential(-3.04 V vs.the standard hydrogen electrode)promise substantially higher energy densities compared to current lithium-ion batteries(LIBs)[1].However,lithium metal electrodes face severe challenges associated with the risk of dendritic lithium deposition and the high reactivity with traditional organic liquid electrolytes,resulting in a continuous loss of electrochemically active lithium and a relatively low Coulombic efficiency[2].To address these challenges,solid inorganic and polymer electrolytes have emerged as a potentially saferalternative.展开更多
Organic electrode materials(OEMs)have attracted substantial attention for aqueous zinc-ion batteries(AZIBs)due to their advantages in relieving resource and environmental anxiety.However,the potential of OEMs is plagu...Organic electrode materials(OEMs)have attracted substantial attention for aqueous zinc-ion batteries(AZIBs)due to their advantages in relieving resource and environmental anxiety.However,the potential of OEMs is plagued by their low achievable capacity and high solubility.Here,we have proposed a new concept of“co-coordination force”and designed a rigid-flexible coupling crystalline polymer that can overcome the abovementioned limitations.The obtained crystalline polymer(BQSPNs)with multiredox centres makes the BQSPNs exist intermolecular hydrogen bonds(HB)among-C=O,-C=N,and-NH and consequently exhibits transverse two-dimensional arrays and longitudinalπ-πstacking structure.Additionally,in-situ FTIR,Raman,variable temperature FTIR spectra,and 2D nuclear overhauser effect spectroscopy(NOESY)well capture the existence and evolution process of HB during the electrochemistry reaction process of BQSPNs,uncovering the effect of HB in stabilizing the structure and promoting the reaction kinetics.As a result,the BQSPNs with rationally designed“co-coordination force”deliver a high capacity of 459.6 m Ah/g and a stable cycling lifetime for more than 100,000 cycles at 10 A/g in AZIBs.Our results disclose the HB effect and provide a brand-new strategy for high-performance OEMs design.展开更多
Lithium metal batteries have been considered as one of the most promising next-generation power-support devices due to their high specific energy and output voltage.However,the uncontrollable side-reaction and lithium...Lithium metal batteries have been considered as one of the most promising next-generation power-support devices due to their high specific energy and output voltage.However,the uncontrollable side-reaction and lithium dendrite growth lead to the limited serving life and hinder the practical application of lithium metal batteries.Here,a tri-monomer copolymerized gel polymer electrolyte(TGPE)with a cross-linked reticulation structure was prepared by introducing a cross-linker(polyurethane group)into the acrylate-based in situ polymerization system.The soft segment of polyurethane in TGPE enables the far migration of lithium ions,and the-NH forms hydrogen bonds in the hard segment to build a stable cross-linked framework.This system hinders anion migration and leads to a high Li^(+)migration number(t_(Li^(+))=0.65),which achieves uniform lithium deposition and effectively inhibits lithium dendrite growth.As a result,the assembled symmetric cell shows robust reversibility over 5500 h at a current density of 1 mA cm^(-2).The LFP∷TGPE∷Li cell has a capacity retention of 89.8%after cycling 800 times at a rate of 1C.In summary,in situ polymerization of TGPE electrolytes is expected to be a candidate material for high-energy-density lithium metal batteries.展开更多
Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(te...Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.展开更多
Electrocatalysts play a crucial role in the performance of rechargeable Zn-air batteries(ZABs),but it is still difficult to produce nonprecious materials with excellent bifunctional oxygen reduction reactions(ORR)and ...Electrocatalysts play a crucial role in the performance of rechargeable Zn-air batteries(ZABs),but it is still difficult to produce nonprecious materials with excellent bifunctional oxygen reduction reactions(ORR)and oxygen evolution reactions(OER).Herein,conjugated polyaniline-phytic acid polymer(pANI-PA)was directly calcined to fabricate Co_(2)P nanoparticles embedded in N,P-doped carbon network composites(Co_(2)P@pDC-PA)for metal-air cathodes.The resulting pANI-PA derived Co_(2)Pbased carbon composite exhibits exceptional bifunctional ORR/OER activities with a half-wave potential of 0.79 V for ORR and 1.62 V of over-potential for OER at 10mA·cm^(-2).Owing to the synergistic effect of its unique three-dimensional(3D)structure,N,P-doped carbon framework,and encapsulated Co_(2)P nanoparticles,as-fabricated composite can be used as a highly efficient air cathode in the rechargeable metal-air battery.The assembled rechargeable ZAB demonstrates a high-power density of 190.0 mW·cm^(-2)and remarkable cycling stability over1000 h.This study introduced a novel approach that paves the way for the efficient,cost-effective,and scalable production of bifunctional electrocatalysts for rechargeable ZABs.展开更多
Satisfactory ionic conductivity,excellent mechanical stability,and high-temperature resistance are the prerequisites for the safe application of solid polymer electrolytes(SPEs)in all-solid-state lithium metal batteri...Satisfactory ionic conductivity,excellent mechanical stability,and high-temperature resistance are the prerequisites for the safe application of solid polymer electrolytes(SPEs)in all-solid-state lithium metal batteries(ASSLMBs).In this study,a novel poly(m-phenylene isophthalamide)(PMIA)-core/poly(ethylene oxide)(PEO)-shell nanofiber membrane and the functional Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)ceramic nanopar-ticle are simultaneously introduced into the PEO-based SPEs to prepare composite polymer electrolytes(CPEs).The core PMIA layer of composite nanofibers can greatly improve the mechanical strength and thermal stability of the CPEs,while the shell PEO layer can provide the 3D continuous transport channels for lithium ions.In addition,the introduction of functional LLZTO nanoparticle not only reduces the crys-tallinity of PEO,but also promotes the dissociation of lithium salts and releases more Li^(+)ions through its interaction with the Lewis acid-base of anions,thereby overall improving the transport of lithium ions.Consequently,the optimized CPEs present high ionic conductivity of 1.38×10^(−4)S/cm at 30℃,signifi-cantly improved mechanical strength(8.5 MPa),remarkable thermal stability(without obvious shrinkage at 150℃),and conspicuous Li dendrites blocking ability(>1800 h).The CPEs also both have good com-patibility and cyclic stability with LiFePO_(4)(>2000 cycles)and high-voltage LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)(>500 cycles)cathodes.In addition,even at low temperature(40℃),the assembled LiFePO4/CPEs/Li bat-tery still can cycle stably.The novel design can provide an effective way to exploit high-performance solid-state electrolytes.展开更多
Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of ni...Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of nitrogen-containing hypercrosslinked fer-rocene polymer precursors(HCP-FCs).Subsequent carbonization of these precursors results in the production of iron-nitrogen-doped por-ous carbon absorbers(Fe-NPCs).The Fe-NPCs demonstrate a porous structure comprising aggregated nanotubes and nanospheres.The porosity of this structure can be modulated by adjusting the iron and nitrogen contents to optimize impedance matching.The uniform dis-tribution of Fe-N_(x)C,N dipoles,andα-Fe within the carbon matrix can be ensured by using hypercrosslinked ferrocenes in constructing porous carbon,providing the absorber with numerous polarization sites and a conductive network.The electromagnetic wave absorption performance of the specially designed Fe-NPC-M_(2)absorbers is satisfactory,revealing a minimum reflection loss of-55.3 dB at 2.5 mm and an effective absorption bandwidth of 6.00 GHz at 2.0 mm.By utilizing hypercrosslinked polymers(HCPs)as precursors,a novel method for developing highly efficient carbon-based absorbing agents is introduced in this research.展开更多
基金supported by National Key Research and Development Program of China(Grant No.2022YFB3809000)Major Science and Technology Project of Gansu Province(Grant No.23ZDGA011)+1 种基金National Natural Science Foundation of China(Grant No.22275199,52105224)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB04701022021).
文摘Compared to subtractive manufacturing and casting,3D printing(additive manufacturing)offers advantages,such as the rapid production of complex structures,reduced material waste,and environmental friendliness.Direct ink writing(DIW)is one of the most popular 3D printing techniques owing to its ability to print multiple materials simultaneously and its high compatibility with printing inks.However,DIW presents significant challenges,particularly in the printing of high-performance polymers.The main challenges are as follows:1.The rigid structures and reaction kinetics of high-performance polymers make developing new inks difficult.2.The limited types of available high-performance polymers underscore the need for new DIW-suitable materials.3.Layer-by-layer stacking weakens interlayer bonding,affecting the mechanical properties of the printed product.4.The accuracy and speed of DIW printing are insufficient for large-scale manufacturing.After introducing the topic,the requirements for DIW printing inks are first reviewed,emphasizing the importance of thixotropic agents.Then,research progress regarding DIW printing of high-performance polymers is comprehensively reviewed according to the requirements of different polymer inks.Additionally,the applications of these materials across various fields are summarized.Finally,the challenges in DIW printing of high-performance polymers,along with corresponding solutions and future development prospects,are discussed in detail.
基金This work was financially supported by the National Natural Science Foundation of China(No.15076017).
文摘Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation reaction.The structures of PIKs are characterized by means of elemental analysis,FT-IR,~1H-NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structure.The general properties of PIKs are studied by DSC,TG and wide-angle X-ray diffraction,the solubility behavior is...
基金The work was financially supported by the Ministry of Science and Technology of China(Nos.2017YFA0206600 and 2019YFA0705900)the National Natural Science Foundation of China(Nos.21875072,U20A6002 and 51973169)+2 种基金Guangdong Innovative and Entrepreneurial Research Team Program(No.2019ZT08L075)This study also received financial support from Science and Technology Foundation of Guangdong Province(No.2021A0101180005)Special Projects in Key Areas for the University of Guangdong Province(No.2021ZDZX1009).
文摘Polymer solar cells(PSCs)consisting of a polymer donor and a small molecular acceptor is a promising photovoltaic technology,whose device performance is determined by both polymer donor and small molecular acceptor.Halogen atoms such as fluorine or chlorine atoms were usually introduced onto the polymer donors to downshift the highest occupied molecular orbital(HOMO)energy levels and improve the open-circuit voltage(VOC)of the PSCs.However,the introduction of the halogen atoms especially fluorine atoms greatly complicates the polymer synthesis.Herein,we report the use of a structural simple and easily synthesized building block,3,4-dicyanothiophene(DCT),to construct a set of halogen-free polymer donors PBCNTx(x=25,50,75)via ternary random copolymerization.The introduction of DCT units not only simplified the synthesis,but also downshifted the HOMO energy levels of the polymers and improved the V_(OC) of PSCs effectively.Encouragingly,the PBCNT75 afforded a power conversion efficiency up to 15.7%with a V_(OC) of 0.83 V,which are among the top values for halogen-free polymer donors.This work shows that the introduction of DCT units is a simple yet effective strategy to construct halogen-free and low-cost polymer donors for high-performance PSCs.
文摘A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.
基金supported by the National Natural Science Foundation of China(51973236,51573213)Zhuhai Industry University-Research Cooperation Program(2320004002721)。
文摘The practical application of poly(ethylene oxide)(PEO)-based solid polymer electrolytes in all-solid-state lithium-metal batteries(ASSLBs)still suffers from persistent challenges associated with low ionic conductivity and poor oxidative stability.To address these issues,we introduce a novel in-situ ionization strategy using radical polymer poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl acrylate)(PTPA)to enhance ionic conductivity and achieve a high electrochemical stability window in PEO-based electrolyte.Density functional theory(DFT)calculations and molecular dynamics(MD)simulations reveal that the in-situ generation of PTPA+from PTPA within the battery,not only exceptionally decreases the low Highest Occupied Molecular Orbital(HOMO)energy level,but also exhibits a robust anchoring effect on TFSI-anions in the electrolyte,which boosts Li^(+) migration and enables dense Li deposition behavior.As a result,the PEO/10 wt%PTPA/LiTFSI electrolyte demonstrates remarkable oxidative stability up to 5 V and a high Li^(+)transference number(0.57).Li-Li symmetric cells maintain stability over 1000 h at 0.2 mA cm^(-2),and LiFePO_(4)(LFP)//Li battery also presents an enduring cyclic performance over 500 cycles with a remarkable high-capacity retention of 91.8% at 0.5C.Impressively,by coupling with a high-voltage LiCoO_(2)(LCO)cathode(cut-off voltage 4.6 V),the assembled ASSLBs reach a capacity retention of 87.1% after 500 cycles at 1C.Our study explores the mechanism of radical polymer in PEO-based electrolyte and provides a fire-new strategy for construction of high-performance and multifunctional ASSLBs.
基金conducted in a project within M-ERA.NET 3 with support from the European Union’s Horizon 2020 research,innovation program under grant agreement No.958174,Vinnova(Swedish Governmental Agency for Innovation Systems)the financial support from the LTU CREATERNITY program+1 种基金the J.Gust Richert Foundationthe National Natural Science Foundation of China(No.U23A20122)。
文摘Quasi-solid-state composite electrolytes(QSCEs)show promise for high-performance solid-state batteries,while they still struggle with interfacial stability and cycling performance.Herein,a F-grafted QSCE(F-QSCE)was developed via copolymerizing the F monomers and ionic liquid monomers.The F-QSCE demonstrates better overall performance,such as high ionic conductivity of 1.21 mS cm^(-1)at 25℃,wide electrochemical windows of 5.20 V,and stable cycling stability for Li//Li symmetric cells over 4000 h.This is attributed to the significant electronegativity difference between C and F in the fluorinated chain(-CF_(2)-CF-CF_(3)),which causes the electron cloud to shift toward the F atom,surrounding it with a negative charge and producing the inductive effect.Furthermore,the interactions between Li^(+)and F,TFSI~-,and C are enhanced,reducing ion pair aggregation(Li^(+)-TFSI~--Li^(+))and promoting Li^(+)transport.Besides,-CF_(2)-CF-CF_(3)decomposes to form Li F preferentially over TFSI~-,resulting in better interfacial stability for F-QSCE.This work provides a pathway to enable the development of high-performance Li metal batteries.
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the Army Research Office under Cooperative Agreement Number W911NF-22-2-0257the National Science Foundation(NSF)Growing Convergence Research program(NSF GCR CMMI 1934887)in Materials Life Cycle Management for financial support during the writing of this manuscript.
文摘CONSPECTUS:Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable,high-performance,polymeric materials.Although lignin is a highly available and low-cost source of natural aromatics,it is commonly burned for heat or disposed of as waste.The use of lignin for new materials introduces both challenges and opportunities with respect to incumbent petrochemical-based compounds.These considerations are derived from two fundamental aspects of lignin:its recalcitrant/heterogeneous nature and aromatic methoxy substituents.
基金supported by the National Natural Science Foundation of China(No.52130101)the Project of Science and Technology Development Plan of Jilin Province in China(Nos.20210402058GH and 20220201114GX)。
文摘Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode,low intrinsic conductivity of sulfur cathode,and severe shuttling effect of sodium polysulfides(NaPSs)pose significant challenges in the actual reversible capacity and cycle life of Na-S batteries.Herein,a self-supporting electrode made of nitrogen-doped carbon fiber embedded with cobalt nanoparticles(Co/NC-CF)is designed to load sulfur.Meanwhile,gel polymer electrolyte(GPE)with high ion transfer ability is obtained by in-situ polymerization inside the battery.During the polymerization process,an integrated electrode-electrolyte and a continuous ion-electron conduction network in a composite cathode are constructed inside the Na-S battery.It is noteworthy that the designed GPE demonstrates superior ionic conductivity and effective adsorption of NaPSs that can significantly suppress the shuttle effect.Leveraging the synergistic interplay between the designed GPE and self-supporting cathode,the assembled quasi-solid-state(QSS)Na-S battery exhibits great cycling stability.These experimental results are further corroborated by COMSOL Multiphysics simulations and density functional theory(DFT)calculations,which mechanistically validate the enhanced electrochemical performance.The findings of this study offer new and promising perspectives for advancing the development of nextgeneration solid-state batteries.
基金supported by the National Natural Science Foundation of China(52372099,52202328,22461142135,22479046)the Shanghai Sailing Program(22YF1455500)the Shanghai Magnolia Talent Plan Pujiang Project(24PJD128)。
文摘Solid-state polymer electrolytes are crucial for advancing solid-state lithium-metal batteries owing to their flexibility,excellent manufacturability,and strong interfacial compatibility.However,their widespread applications are hindered by low ionic conductivity at room temperature and lithium dendrite growth.Herein,we report a novel solid-state composite membrane electrolyte design that combines the vertically aligned channel structure and copolymer with a radial gradient composition.Within the vertically aligned channels,the composition of poly(vinyl ethylene carbonate-co-poly(ethylene glycol)diacrylate)(P(VEC-PEGDA)varies in a gradient along the radial direction:from the center to the wall of vertically aligned channels,the proportion of vinyl ethylene carbonate(VEC)in the copolymer decreases,while the proportion of poly(ethylene glycol)diacrylate(PEGDA)increases accordingly.It can be functionally divided into a mechanical-reinforcement layer and a fast-ion-conducting layer.The resulting solid-state composite membrane electrolyte achieves a high critical current density of 1.2 mA cm^(-2)and high ionic conductivity of 2.03 mS cm^(-1)at room temperature.Employing this composite membrane electrolyte,a Li//Li symmetric cell exhibits stable cycling for over 1850 h at 0.2 m A cm^(-2)/0.2 m A h cm^(-2),and a Li//LiFePO4(LFP)battery maintains 77.3% capacity retention at 2 C after 300 cycles.Our work provides insight into the rational design of safer and more efficient solidstate batteries through electrolyte structural engineering.
基金Natural Science Foundation of China (51603031)Liaoning Provincial Natural Science Foundation of China (2020-MS-087)China Scholarship Council(202306080157)。
文摘This work focuses on the development of high temperature polymer electrolyte membranes(HT-PEMs)as key materials for HT-PEM fuel cells(HT-PEMFCs).Recognizing the challenges associated with the phosphoric acid(PA) doped polybenzimidazole(PBI) membranes,including the use of carcinogenic monomers and complex synthesis procedures,this study aims to develop more cost-effective,readily synthesized,and high-performance alternatives.A series of superacid-catalyzed polyhydroxyalkylation reactions have been carefully designed between p-terphenyl and aldehydes bearing imidazole moieties,resulting in a new class of HT-PEMs.It is found that the chemical structure of aldehyde-substituted N-heterocycles significantly impacts the polymerization reaction.Specifically,the use of 1-methyl-2-imidazole-formaldehyde and 1 H-imidazole-4-formaldehyde monomers leads to the formation of high-viscosity,rigid,and ether-free polymers,denoted as PTIm-a and PTIm-b.Membranes fabricated from these polymers,due to their pendent imidazole groups,exhibit an exceptional capacity for PA absorption.Notably,PTIm-a,carrying methylimidazole moieties,demonstrates a superior chemical stability by maintaining morphology and structural stability during 350 h of Fenton testing.After being immersed in 75 wt% PA at 40℃,the PTIm-a membrane reaches a PA content of 152%,maintains a good tensile strength of 13.6 MPa,and exhibits a moderate conductivity of 50.2 mS cm^(-1) at 180℃.Under H_(2)/O_(2) operational conditions,a single cell based on the PTIm-a membrane attains a peak power density of 732 mW cm^(-2) at 180℃ without backpressure.Furthermore,the membrane demonstrates stable cycle stability over 173 h within 18 days at a current density of 200 mA cm^(-2),indicating its potential for practical application in HT-PEMFCs.This work highlights innovative strategies for the synthesis of advanced HT-PEMs,offering significant improvements in membrane properties and fuel cell performance,thus expanding the horizons of HT-PEMFC technology.
基金supported by the National Natural Science Foundation of China(22071021).
文摘To address the issues in aqueous zinc-ion batteries(ZIBs),including the formation of zinc dendrites and the occurrence of harmful side reactions(e.g.,the hydrogen evolution reaction),which seriously affect the performance of the battery,a sulfonated covalent organic framework(SCOF),TpPa-SO3H,was synthesized and the quasi-solid polymer electrolyte SCOF-PVDF/Zn(CF3SO3)2 was successfully prepared with a polymer matrix of PVDF and an ion-transporting backbone of SCOF.Both of Zn//Zn symmetric batteries and Zn//NH4V4O10 full batteries assembled using SCOF-PVDF/Zn(CF3SO3)2 electrolyte exhibited excellent battery cycling stability.The high ionic conductivity of 3×10^(-4)S·cm^(-1)could be achieved.The assembled symmetric batteries demonstrated a cycle life of 980 h at a current density of 2 mA·cm^(-2).The Zn//NH4V4O10 full battery can provide a specific capacity of 196 mAh·g^(-1)at a high current density of 10 A·g^(-1).
基金National Natural Science Foundation of China (22222902, 22209062)Natural Science Foundation of the Jiangsu Higher Education Institutions of China (22KJB150004)+1 种基金Youth Talent Promotion Project of Jiangsu Association for Science and Technology of China (JSTJ-2022-023)Undergraduate Innovation and Entrepreneurship Training Program (202310320066Z)。
文摘In the pursuit of ultrathin polymer electrolyte(<20 μm) for lithium metal batteries, achieving a balance between mechanical strength and interfacial stability is crucial for the longevity of the electrolytes.Herein, 11 μm-thick gel polymer electrolyte is designed via an integrated electrode/electrolyte structure supported by lithium metal anode. Benefiting from an exemplary superiority of excellent mechanical property, high ionic conductivity, and robust interfacial adhesion, the in-situ formed polymer electrolyte reinforced by titanosiloxane networks(ISPTS) embodies multifunctional roles of physical barrier, ionic carrier, and artificial protective layer at the interface. The potent interfacial interactions foster a seamless fusion of the electrode/electrolyte interfaces and enable continuous ion transport. Moreover, the built-in ISPTS electrolyte participates in the formation of gradient solid-electrolyte interphase(SEI) layer, which enhances the SEI's structural integrity against the strain induced by volume fluctuations of lithium anode.Consequently, the resultant 11 μm-thick ISPTS electrolyte enables lithium symmetric cells with cycling stability over 600 h and LiFePO_(4) cells with remarkable capacity retention of 96.6% after 800 cycles.This study provides a new avenue for designing ultrathin polymer electrolytes towards stable, safe,and high-energy–density lithium metal batteries.
基金financial support from the Federal Ministry of Education and Research (BMBF) within the FestBatt project (03XP0175B)the FB2-Poly project(03XP0429B)the Helmholtz Association
文摘The continuously growing importance of batteries for powering(hybrid)electric vehicles and storing renewable energy has prompted a renewed focus on lithium-metal batteries(LMBs)in recent years,as its high theoretical specific capacity of about 3860 mA h g^(-1) and very low redox potential(-3.04 V vs.the standard hydrogen electrode)promise substantially higher energy densities compared to current lithium-ion batteries(LIBs)[1].However,lithium metal electrodes face severe challenges associated with the risk of dendritic lithium deposition and the high reactivity with traditional organic liquid electrolytes,resulting in a continuous loss of electrochemically active lithium and a relatively low Coulombic efficiency[2].To address these challenges,solid inorganic and polymer electrolytes have emerged as a potentially saferalternative.
基金financially supported by the National Key R&D program of China(No.2022YFB2402200)National Natural Science Foundation of China(Nos.52271140,52171194)+2 种基金Youth Innovation Promotion Association CAS(No.2020230)Jilin Provincial NaturalFund(No.20230101205JC)National Natural Science Foundation of China Outstanding Youth Science Foundation of China(Overseas)。
文摘Organic electrode materials(OEMs)have attracted substantial attention for aqueous zinc-ion batteries(AZIBs)due to their advantages in relieving resource and environmental anxiety.However,the potential of OEMs is plagued by their low achievable capacity and high solubility.Here,we have proposed a new concept of“co-coordination force”and designed a rigid-flexible coupling crystalline polymer that can overcome the abovementioned limitations.The obtained crystalline polymer(BQSPNs)with multiredox centres makes the BQSPNs exist intermolecular hydrogen bonds(HB)among-C=O,-C=N,and-NH and consequently exhibits transverse two-dimensional arrays and longitudinalπ-πstacking structure.Additionally,in-situ FTIR,Raman,variable temperature FTIR spectra,and 2D nuclear overhauser effect spectroscopy(NOESY)well capture the existence and evolution process of HB during the electrochemistry reaction process of BQSPNs,uncovering the effect of HB in stabilizing the structure and promoting the reaction kinetics.As a result,the BQSPNs with rationally designed“co-coordination force”deliver a high capacity of 459.6 m Ah/g and a stable cycling lifetime for more than 100,000 cycles at 10 A/g in AZIBs.Our results disclose the HB effect and provide a brand-new strategy for high-performance OEMs design.
基金support from the National Natural Science Foundation of China(52077096)
文摘Lithium metal batteries have been considered as one of the most promising next-generation power-support devices due to their high specific energy and output voltage.However,the uncontrollable side-reaction and lithium dendrite growth lead to the limited serving life and hinder the practical application of lithium metal batteries.Here,a tri-monomer copolymerized gel polymer electrolyte(TGPE)with a cross-linked reticulation structure was prepared by introducing a cross-linker(polyurethane group)into the acrylate-based in situ polymerization system.The soft segment of polyurethane in TGPE enables the far migration of lithium ions,and the-NH forms hydrogen bonds in the hard segment to build a stable cross-linked framework.This system hinders anion migration and leads to a high Li^(+)migration number(t_(Li^(+))=0.65),which achieves uniform lithium deposition and effectively inhibits lithium dendrite growth.As a result,the assembled symmetric cell shows robust reversibility over 5500 h at a current density of 1 mA cm^(-2).The LFP∷TGPE∷Li cell has a capacity retention of 89.8%after cycling 800 times at a rate of 1C.In summary,in situ polymerization of TGPE electrolytes is expected to be a candidate material for high-energy-density lithium metal batteries.
基金supported by The National Key Research and Development Program of China(2021YFB4001204)National Natural Science Foundation of China(22379143)。
文摘Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.
基金financially supported by Hubei Provincial Natural Science Foundation and Huangshi of China(No.2022CFD039)the National Natural Science Foundation of China(Nos.22075072,52202284 and 52301272)+6 种基金the College Students Innovation and Entrepreneurship Training Program of China(Nos.D202305271035223001,D202305271407085899 and D202305272109110950)Zhejiang Provincial Natural Science Foundation(No.LQ23E020002)Wenzhou Key Scientific and Technological Innovation Research Projects(No.ZG2023053)Wenzhou Natural Science Foundation(Nos.ZG2022032,G20220019 and G20220021)the Cooperation between Industry and Education Project of Ministry of Education(No.220601318235513)the State Key Laboratory of Electrical Insulation and Power Equipment,Xi'an Jiaotong University(No.EIPE22208)the Doctoral Innovation Foundation of Wenzhou University(No.3162023001001)。
文摘Electrocatalysts play a crucial role in the performance of rechargeable Zn-air batteries(ZABs),but it is still difficult to produce nonprecious materials with excellent bifunctional oxygen reduction reactions(ORR)and oxygen evolution reactions(OER).Herein,conjugated polyaniline-phytic acid polymer(pANI-PA)was directly calcined to fabricate Co_(2)P nanoparticles embedded in N,P-doped carbon network composites(Co_(2)P@pDC-PA)for metal-air cathodes.The resulting pANI-PA derived Co_(2)Pbased carbon composite exhibits exceptional bifunctional ORR/OER activities with a half-wave potential of 0.79 V for ORR and 1.62 V of over-potential for OER at 10mA·cm^(-2).Owing to the synergistic effect of its unique three-dimensional(3D)structure,N,P-doped carbon framework,and encapsulated Co_(2)P nanoparticles,as-fabricated composite can be used as a highly efficient air cathode in the rechargeable metal-air battery.The assembled rechargeable ZAB demonstrates a high-power density of 190.0 mW·cm^(-2)and remarkable cycling stability over1000 h.This study introduced a novel approach that paves the way for the efficient,cost-effective,and scalable production of bifunctional electrocatalysts for rechargeable ZABs.
基金supported by the National Natural Science Foundation of China (Nos.52203066,51973157,61904123)the Tianjin Natural Science Foundation (No.18JCQNJC02900)+3 种基金National Innovation and Entrepreneurship Training Program for College students (No.202310058007)Tianjin Municipal College Students’ Innovation and Entrepreneurship Training Program (No.202310058088)Science & Technology Development Fund of Tianjin Education Commission for Higher Education (No.2018KJ196)State Key Laboratory of Membrane and Membrane Separation,Tiangong University
文摘Satisfactory ionic conductivity,excellent mechanical stability,and high-temperature resistance are the prerequisites for the safe application of solid polymer electrolytes(SPEs)in all-solid-state lithium metal batteries(ASSLMBs).In this study,a novel poly(m-phenylene isophthalamide)(PMIA)-core/poly(ethylene oxide)(PEO)-shell nanofiber membrane and the functional Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)ceramic nanopar-ticle are simultaneously introduced into the PEO-based SPEs to prepare composite polymer electrolytes(CPEs).The core PMIA layer of composite nanofibers can greatly improve the mechanical strength and thermal stability of the CPEs,while the shell PEO layer can provide the 3D continuous transport channels for lithium ions.In addition,the introduction of functional LLZTO nanoparticle not only reduces the crys-tallinity of PEO,but also promotes the dissociation of lithium salts and releases more Li^(+)ions through its interaction with the Lewis acid-base of anions,thereby overall improving the transport of lithium ions.Consequently,the optimized CPEs present high ionic conductivity of 1.38×10^(−4)S/cm at 30℃,signifi-cantly improved mechanical strength(8.5 MPa),remarkable thermal stability(without obvious shrinkage at 150℃),and conspicuous Li dendrites blocking ability(>1800 h).The CPEs also both have good com-patibility and cyclic stability with LiFePO_(4)(>2000 cycles)and high-voltage LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)(>500 cycles)cathodes.In addition,even at low temperature(40℃),the assembled LiFePO4/CPEs/Li bat-tery still can cycle stably.The novel design can provide an effective way to exploit high-performance solid-state electrolytes.
基金supported by the National Natural Science Foundation of China(No.51803041)the University and Local Integration Development Project of Yantai,China(No.2022 XDRHXMXK08).
文摘Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of nitrogen-containing hypercrosslinked fer-rocene polymer precursors(HCP-FCs).Subsequent carbonization of these precursors results in the production of iron-nitrogen-doped por-ous carbon absorbers(Fe-NPCs).The Fe-NPCs demonstrate a porous structure comprising aggregated nanotubes and nanospheres.The porosity of this structure can be modulated by adjusting the iron and nitrogen contents to optimize impedance matching.The uniform dis-tribution of Fe-N_(x)C,N dipoles,andα-Fe within the carbon matrix can be ensured by using hypercrosslinked ferrocenes in constructing porous carbon,providing the absorber with numerous polarization sites and a conductive network.The electromagnetic wave absorption performance of the specially designed Fe-NPC-M_(2)absorbers is satisfactory,revealing a minimum reflection loss of-55.3 dB at 2.5 mm and an effective absorption bandwidth of 6.00 GHz at 2.0 mm.By utilizing hypercrosslinked polymers(HCPs)as precursors,a novel method for developing highly efficient carbon-based absorbing agents is introduced in this research.
