Proton-conducting materials have attracted considerable interest because of their extensive application in energy storage and conversion devices.Among them,metal-organic frameworks(MOFs)present tremendous development ...Proton-conducting materials have attracted considerable interest because of their extensive application in energy storage and conversion devices.Among them,metal-organic frameworks(MOFs)present tremendous development potential and possibilities for constructing novel advanced proton conductors due to their special advantages in crystallinity,designability,and porosity.In particular,several special design strategies for the structure of MOFs have opened new doors for the advancement of MOF proton conductors,such as charged network construction,ligand functionalization,metal-center manipulation,defective engineering,vip molecule incorporation,and pore-space manipulation.With the implementation of these strategies,proton-conducting MOFs have developed significantly and profoundly within the last decade.Therefore,in this review,we critically discuss and analyze the fundamental principles,design strategies,and implementation methods targeted at improving the proton conductivity of MOFs through representative examples.Besides,the structural features,the proton conduction mechanism and the behavior of MOFs are discussed thoroughly and meticulously.Future endeavors are also proposed to address the challenges of proton-conducting MOFs in practical research.We sincerely expect that this review will bring guidance and inspiration for the design of proton-conducting MOFs and further motivate the research enthusiasm for novel proton-conducting materials.展开更多
Two-dimensional carbon-based materials have shown promising electromagnetic wave absorption capabilities in mid-and high-frequency ranges,but face challenges in low-frequency absorption due to limited control over pol...Two-dimensional carbon-based materials have shown promising electromagnetic wave absorption capabilities in mid-and high-frequency ranges,but face challenges in low-frequency absorption due to limited control over polarization response mecha-nisms and ambiguous resonance behavior.In this study,we pro-pose a novel approach to enhance absorption efficiency in aligned three-dimensional(3D)MXene/CNF(cellulose nanofibers)cavities by modifying polarization properties and manipulating resonance response in the 3D MXene architecture.This controlled polarization mechanism results in a significant shift of the main absorption region from the X-band to the S-band,leading to a remarkable reflection loss value of-47.9 dB in the low-frequency range.Furthermore,our findings revealed the importance of the oriented electromagnetic coupling in influencing electromagnetic response and microwave absorption properties.The present study inspired us to develop a generic strategy for low-frequency tuned absorption in the absence of magnetic element participation,while orientation-induced polarization and the derived magnetic resonance coupling are the key controlling factors of the method.展开更多
Multifunctional architecture with intriguing structural design is highly desired for realizing the promising performances in wearable sensors and flexible energy storage devices.Cellulose nanofiber(CNF)is employed for...Multifunctional architecture with intriguing structural design is highly desired for realizing the promising performances in wearable sensors and flexible energy storage devices.Cellulose nanofiber(CNF)is employed for assisting in building conductive,hyperelastic,and ultralight Ti_(3)C_(2)T_(x)MXene hybrid aerogels with oriented tracheid-like texture.The biomimetic hybrid aerogels are constructed by a facile bidirectional freezing strategy with CNF,carbon nanotube(CNT),and MXene based on synergistic electrostatic interaction and hydrogen bonding.Entangled CNF and CNT“mortars”bonded with MXene“bricks”of the tracheid structure produce good interfacial binding,and superior mechanical strength(up to 80%compressibility and extraordinary fatigue resistance of 1000 cycles at 50%strain).Benefiting from the biomimetic texture,CNF/CNT/MXene aerogel shows ultralow density of 7.48 mg cm^(-3)and excellent electrical conductivity(~2400 S m^(-1)).Used as pressure sensors,such aerogels exhibit appealing sensitivity performance with the linear sensitivity up to 817.3 kPa^(-1),which affords their application in monitoring body surface information and detecting human motion.Furthermore,the aerogels can also act as electrode materials of compressive solid-state supercapacitors that reveal satisfactory electrochemical performance(849.2 mF cm^(-2)at 0.8 mA cm^(-2))and superior long cycle compression performance(88%after 10,000 cycles at a compressive strain of 30%).展开更多
Poly(ethylene terephthalate) (PET)/carbon black (CB) masterbatch was prepared by melt blending using a separate feeding technique and its homogeneous dispersion morphology was confirmed by transmission electron micros...Poly(ethylene terephthalate) (PET)/carbon black (CB) masterbatch was prepared by melt blending using a separate feeding technique and its homogeneous dispersion morphology was confirmed by transmission electron microscope (TEM). The Avrami and Hoffman-Lauritzen secondary nucleation theories were employed to analyze the effect of high CB content on crystallization kinetics of PET, providing theoretical support for the development of masterbatch with high content of functional components. The Avrami exponents,average values of n,for PET and PET/CB masterbatch are both greater than 3, which indicates three-dimensional growth of crystals. In addition,no significant evidence for regime transition of PET is found applying Hoffman-Lauritzen secondary nucleation theory,though such observations have been reported previously in the literature. Furthermore,appropriate U* value for PET is determined to be 12 800 J/mol. For PET/CB masterbatch,a transition from regime I to regime II around 225℃ is observed with appropriate U* value (12 800 J/mol) . This phenomenon is consistent with a transition point in plot of G versus Tc . The fold surface free energy σe (100. 3 mJ/m 2) of PET is much greater than that of PET/CB masterbatch (48. 3 mJ/m 2) ,which indicates heterogeneous nucleation effect of CB particles.展开更多
Considering the serious barriers/issues induced by the accumulated starch generated in white water system of old corrugated cardboard(OCC)pulping process,large amounts of accumulated starch in white water would be dec...Considering the serious barriers/issues induced by the accumulated starch generated in white water system of old corrugated cardboard(OCC)pulping process,large amounts of accumulated starch in white water would be decomposed by microorganisms and could not be utilized,thereby resulting in severe resource wastage and environmental pollution.This study mainly explored the effects of biodegradation/hydrolysis conditions of the two types of starch substrates(native starch and enzymatically(α-amylase)hydrolyzed starch),which were treated via microorganism degradation within the simulated white water from OCC pulping system and their biodegradation products on the key properties were characterized via X-ray diffraction(XRD),Fourier-transform infrared spectroscopy(FT-IR),and gel permeation chromatography(GPC)technologies.The effects of system temperature,pH value,starch concentration,and biodegradation time on starch biodegradation ratio and the characteristics of obtained biodegradated products from the two types of starches were studied.In addition,the effect ofα-amylase dosage on the biodegradation ratio of enzymatically hydrolyzed starch and its properties was investigated.It was found that the native starch presented a maximal degradation ratio at a system temperature of 55℃and pH value range of 5-7,respectively,the corresponding starch concentration within simulated white water system was 200 mg/L.Whereas the enzymatically hydrolyzed starch exhibited a highest degradation ratio at a system temperature of 50℃and pH value of 5.5,respectively,and the corresponding starch concentration within simulated white water system was 100 mg/L.It was verified that native starch is more readily bio-hydrolyzed and biodegradation-susceptive by microorganisms in simulated white water system of OCC pulping process,while the enzymatically hydrolyzed starch exhibits better biodegradation/hydrolysis resistance to the microbial degradation than that of native starch.This study provides a practical and interesting approach to investigate the starch hydrolysis or biodegradation behaviors in white water system of OCC pulping process,which would greatly contribute to the full recycling and valorized application of starch as a versatile additive during paperboard production.展开更多
Suppression of uncontrollable dendrite growth and water-induced side reactions of Zn metal anodes is crucial for achieving long-lasting cycling stability and facilitating the practical implementations of aqueous Zn-me...Suppression of uncontrollable dendrite growth and water-induced side reactions of Zn metal anodes is crucial for achieving long-lasting cycling stability and facilitating the practical implementations of aqueous Zn-metal batteries.To address these challenges,we report in this study a functional nitro-cellulose interfacial layer(NCIL)on the surface of Zn anodes enlightened by a nitro-coordination chemistry strategy.The NCIL exhibits strong zincophilicity and superior coordination capability with Zn^(2+)due to the highly electronegative and highly nucleophilic nature of the nitro functional group.This characteristic facilitates a rapid Zn-ion desolvation process and homogeneous Zn plating,effectively preventing H_(2) evolution and dendrite formation.Additionally,the negatively charged surface of NCIL acts as a shield,repelling SO_(4)^(2-)anions and inhibiting corrosive reactions on the Zn surface.Remarkably,reversible and stable Zn plating/stripping is achieved for over 5100 h at a current density of 1 mA cm^(-2),which is nearly 30 times longer than that of bare Zn anodes.Furthermore,the Zn/V_(2)O_(5) full cells with the functional interface layer deliver a high-capacity retention of 80.3%for over 10,000 cycles at 5 A g^(-1).This research offers valuable insights for the rational development of advanced protective interface layers in order to achieve ultra-long-lifeZnmetal batteries.展开更多
The low ionic conductivities,poor high-voltage stabilities,and lithium dendrite formation of polymer solid electrolytes preclude their use in all-solid-state lithium metal batteries(ASSLMBs).This work provides a simpl...The low ionic conductivities,poor high-voltage stabilities,and lithium dendrite formation of polymer solid electrolytes preclude their use in all-solid-state lithium metal batteries(ASSLMBs).This work provides a simple and scalable technique for constructing fast ion conductor nanofibers(FICNFs)and poly-m-phenyleneisophthalamide(PMIA)nanofibers synergistically enhanced polyethylene oxide(PEO)-based composite solid electrolytes(CSEs)for ASSLMBs.The FICNFs,which were mainly composed of high loadings of ZrO_(2)or Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)nanoparticles,had a percolated ceramic phase inside the nanofibers,while the exposed nanoparticles formed continuous organic–inorganic interfaces with the PEO matrix to enable Li+transport.The interfacial transport rate between ZrO_(2)and PEO was calculated as 4.78×10^(–5)cm^(2)s^(−1)with ab initio molecular dynamics(AIMD)simulations.Besides,the PMIA nanofibers provided strong skeletal support for the CSEs,ensuring excellent mechanical strength and safety for thin CSEs even at high temperatures.More importantly,the amide groups in PMIA provided abundant hydrogen bonds with TFSI−,which lowered the lowest unoccupied molecular orbital(LUMO)level of lithium salts,thus promoting the generation of lithium fluoride-rich solid electrolyte interphase.Consequently,the modified CSEs exhibited satisfactory ionic conductivities(5.38×10^(–4)S cm^(−1)at 50℃)and notable Li dendrite suppression(>1500 h at 0.3 mAh cm^(−2)).The assembled LiFePO_(4)||Li full cells display ultra-long cycles(>2000 cycles)at 50℃ and 40℃.More strikingly,the LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)||Li cell also can stably run for 500 cycles,and the LiFePO_(4)||Li flexible pouch cells also cycled normally,demonstrating tremendous potential for practical application.展开更多
The advancement of direct seawater electrolysis is a significant step towards sustainable hydrogen production,addressing the critical need for renewable energy sources and efficient resource utilization.However,direct...The advancement of direct seawater electrolysis is a significant step towards sustainable hydrogen production,addressing the critical need for renewable energy sources and efficient resource utilization.However,direct seawater electrolysis has to face several challenges posed by the corrosiveness of highly concentrated chloride and the competitive chlorine evolution reaction(ClER).To overcome these issues,we designed a novel NiP_(2)@CoP electrocatalyst on a porous titanium microfiltration(Ti MF)membrane.The obtained bifunctional NiP_(2)@CoP catalyst outperforms the Pt/C and IrO_(2),as evidenced by its low overpotentials of 192 and 425 mV at a current density of 500 mA·cm^(-2) for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in alkaline seawater(1 M KOH+0.5 M NaCl),respectively.Especially,only 231 and 569 mV overpotentials are required at the current density of 1500 mA·cm^(-2) towards HER and OER in alkaline seawater,respectively.More importantly,no ClER was observed,demonstrating its excellent selectivity to OER.The selection of porous Ti MF membrane as an electrode substrate further enhances the performance by providing a robust structure that promotes the fast generation and release of gas bubbles.Our promising outcomes obtained with NiP_(2)@CoP catalysts on Ti MF support,therefore,pave the way for the commercial viability of direct seawater electrolysis technologies at industrial-level current densities.展开更多
Polyglycolide (PGA) fibers applied as surgical sutures strongly depend on their microstructure. The structural evolution of PGA nascent fibers during single low-temperature stretching and segmented high-temperature st...Polyglycolide (PGA) fibers applied as surgical sutures strongly depend on their microstructure. The structural evolution of PGA nascent fibers during single low-temperature stretching and segmented high-temperature stretching was analyzed based on a combination of in situ WAXD/SAXS and DSC measurements. The results indicated that the hot stretching was conducive to the crystal perfection and the local fragmentation and recrystallization of the lamellar crystals may occur under stress induction. The single low-temperature stretching of PGA nascent fibers could be divided into three stages: the stretching of amorphous regions, stretch-induced crystallization and the stretching of crystalline regions. The elongation at break of the fibers can be substantially increased by adopting a segmented stretching method, and the high-temperature stretching can also significantly increase the crystallinity and orientation. The amorphous orientation peak appearing in the low-temperature stretching was gradually converted to crystallization peak during the heating process, which greatly improved the crystallinity and orientation of the fibers. High-temperature stretching compared with low-temperature stretching was more favorable for crystal perfection and structural evolution, where lamellar crystals underwent stress-induced fragmentation recrystallization to transform to fibrous crystals as the strain increased.展开更多
The electrochemical oxidation of 5-hydroxymethylfurfural(HMF)to valuable chemicals is an efficient way to upgrade biomass molecules and replace traditional catalytic synthesis.It is crucial to develop efficient and lo...The electrochemical oxidation of 5-hydroxymethylfurfural(HMF)to valuable chemicals is an efficient way to upgrade biomass molecules and replace traditional catalytic synthesis.It is crucial to develop efficient and low-cost earth-abundant electrocatalysts to enhance catalytic performance of HMF oxidation.Herein,a new type of two-dimensional(2D)hybrid arrays consisting of Ni Fe layered double hydroxides(LDH)nanosheets and bimetallic sulfide(Ni Fe S)is constructed via interface engineering for efficient electrocatalytic oxidation of HMF to 2,5-furandicarboxylic acid(FDCA).The preparation process of 2D Ni Fe LDH/NiFeS with ultrathin heterostructure involves in anchoring a Co-based metal-organic framework(Co MOF)as template onto the carbon cloth(CC)via in-situ growth,formation of NiFe LDH on the surface of Co MOF and subsequent partial sulfidation.The electrocatalyst of Ni Fe LDH/Ni Fe S exhibits outstanding performance towards HMF oxidation,about 98.5%yield for FDCA and 97.2%Faraday efficiency(FE)in the alkaline electrolyte with 10 mmol/L HMF,as well as excellent stability retaining 90.1%FE for FDCA after six cycles test.Moreover,even at an HMF concentration of 100 mmol/L,the yield and FE for FDCA remain high at 83.6%and 93.6%,respectively.These findings highlight that 2D heterostructure containing abundant interfaces between Ni Fe LDH nanosheets and Ni Fe S can enhance the intrinsic activity of LDH and thus promote the oxidation reaction kinetics.Additionally,the synergistic effect of the bimetallic Ni Fe compounds also improved the selectivity of HMF conversion to FDCA.Our present work demonstrates that constructing 2D ultrathin heterostructure of Ni Fe LDH/Ni Fe S is a facile strategy via interface engineering to enhance the intrinsic activity of LDH electrocatalysts,which would open new avenues toward low-cost and advanced 2D nanocatalysts for sustainable energy conversion and electrochemical valorization of biomass derivatives.展开更多
Supercapacitors exhibit considerable potential as energy storage devices due to their high power density,fast charging and discharging abilities,long cycle life,and ecofriendliness.With the increasing environmental co...Supercapacitors exhibit considerable potential as energy storage devices due to their high power density,fast charging and discharging abilities,long cycle life,and ecofriendliness.With the increasing environmental concerns associated with synthetic compounds,the use of environment friendly biopolymers to replace conventional petroleum-based materials has been widely studied.Biomass-based materials are biodegradable,renewable,environment friendly and non-toxic.The unique hierarchical nanostructure,excellent mechanical properties and hydrophilicity allow them to be used to create functional conductive materials with precisely controlled structures and different properties.In this review,the latest development of biomass-based supercapacitor materials is reviewed and discussed.This paper describes the physical and chemical properties of various biopolymers and their impact on supercapacitors,as well as the classification and basic principles of supercapacitors.Then,a comprehensive discussion is presented on the utilization of biomass-based materials in supercapacitors and their recent applications across a range of supercapacitor devices.Finally,an overview of the future prospects and challenges pertaining to the utilization of biomass-based materials in supercapacitors is provided.展开更多
基金supported by the China Scholarship Council(No.202408120105)National Natural Science Foundation of China(32301530)+5 种基金Young Elite Scientist Sponsorship Program by CAST(No.YESS20230242)Tianjin Excellent Special Commissioner for Agricultural Science and Technology Project(23ZYCGSN00580)Natural Science Foundation of Tianjin(23JCZDJC00630)China Postdoctoral Science Foundation(2023M740563)State Key Laboratory of Pulp and Paper Engineering(202412,202413)the Central Publicinterest Scientific Institution Basa Research Fund(No.Y2022QC30).
文摘Proton-conducting materials have attracted considerable interest because of their extensive application in energy storage and conversion devices.Among them,metal-organic frameworks(MOFs)present tremendous development potential and possibilities for constructing novel advanced proton conductors due to their special advantages in crystallinity,designability,and porosity.In particular,several special design strategies for the structure of MOFs have opened new doors for the advancement of MOF proton conductors,such as charged network construction,ligand functionalization,metal-center manipulation,defective engineering,vip molecule incorporation,and pore-space manipulation.With the implementation of these strategies,proton-conducting MOFs have developed significantly and profoundly within the last decade.Therefore,in this review,we critically discuss and analyze the fundamental principles,design strategies,and implementation methods targeted at improving the proton conductivity of MOFs through representative examples.Besides,the structural features,the proton conduction mechanism and the behavior of MOFs are discussed thoroughly and meticulously.Future endeavors are also proposed to address the challenges of proton-conducting MOFs in practical research.We sincerely expect that this review will bring guidance and inspiration for the design of proton-conducting MOFs and further motivate the research enthusiasm for novel proton-conducting materials.
基金financial support from National Key R&D Program of China(MoST,2020YFA0711500)the National Natural Science Foundation of China(NSFC,21875114),(NSFC,52303348)+1 种基金111 Project(B18030)“The Fundamental Research Funds for the Central Universities”,Nankai University.
文摘Two-dimensional carbon-based materials have shown promising electromagnetic wave absorption capabilities in mid-and high-frequency ranges,but face challenges in low-frequency absorption due to limited control over polarization response mecha-nisms and ambiguous resonance behavior.In this study,we pro-pose a novel approach to enhance absorption efficiency in aligned three-dimensional(3D)MXene/CNF(cellulose nanofibers)cavities by modifying polarization properties and manipulating resonance response in the 3D MXene architecture.This controlled polarization mechanism results in a significant shift of the main absorption region from the X-band to the S-band,leading to a remarkable reflection loss value of-47.9 dB in the low-frequency range.Furthermore,our findings revealed the importance of the oriented electromagnetic coupling in influencing electromagnetic response and microwave absorption properties.The present study inspired us to develop a generic strategy for low-frequency tuned absorption in the absence of magnetic element participation,while orientation-induced polarization and the derived magnetic resonance coupling are the key controlling factors of the method.
基金supported by the Project of Jinan City(202228044)National Natural Science Foundation of China(32071720,32271814)+1 种基金the China Postdoctoral Science Foundation(2021M702456)China Scholarship Council for supporting their PhD program。
文摘Multifunctional architecture with intriguing structural design is highly desired for realizing the promising performances in wearable sensors and flexible energy storage devices.Cellulose nanofiber(CNF)is employed for assisting in building conductive,hyperelastic,and ultralight Ti_(3)C_(2)T_(x)MXene hybrid aerogels with oriented tracheid-like texture.The biomimetic hybrid aerogels are constructed by a facile bidirectional freezing strategy with CNF,carbon nanotube(CNT),and MXene based on synergistic electrostatic interaction and hydrogen bonding.Entangled CNF and CNT“mortars”bonded with MXene“bricks”of the tracheid structure produce good interfacial binding,and superior mechanical strength(up to 80%compressibility and extraordinary fatigue resistance of 1000 cycles at 50%strain).Benefiting from the biomimetic texture,CNF/CNT/MXene aerogel shows ultralow density of 7.48 mg cm^(-3)and excellent electrical conductivity(~2400 S m^(-1)).Used as pressure sensors,such aerogels exhibit appealing sensitivity performance with the linear sensitivity up to 817.3 kPa^(-1),which affords their application in monitoring body surface information and detecting human motion.Furthermore,the aerogels can also act as electrode materials of compressive solid-state supercapacitors that reveal satisfactory electrochemical performance(849.2 mF cm^(-2)at 0.8 mA cm^(-2))and superior long cycle compression performance(88%after 10,000 cycles at a compressive strain of 30%).
文摘Poly(ethylene terephthalate) (PET)/carbon black (CB) masterbatch was prepared by melt blending using a separate feeding technique and its homogeneous dispersion morphology was confirmed by transmission electron microscope (TEM). The Avrami and Hoffman-Lauritzen secondary nucleation theories were employed to analyze the effect of high CB content on crystallization kinetics of PET, providing theoretical support for the development of masterbatch with high content of functional components. The Avrami exponents,average values of n,for PET and PET/CB masterbatch are both greater than 3, which indicates three-dimensional growth of crystals. In addition,no significant evidence for regime transition of PET is found applying Hoffman-Lauritzen secondary nucleation theory,though such observations have been reported previously in the literature. Furthermore,appropriate U* value for PET is determined to be 12 800 J/mol. For PET/CB masterbatch,a transition from regime I to regime II around 225℃ is observed with appropriate U* value (12 800 J/mol) . This phenomenon is consistent with a transition point in plot of G versus Tc . The fold surface free energy σe (100. 3 mJ/m 2) of PET is much greater than that of PET/CB masterbatch (48. 3 mJ/m 2) ,which indicates heterogeneous nucleation effect of CB particles.
基金financial support from the China Postdoctoral Science Foundation (No. 2022M712379, No. 2021M692401)National Natural Science Foundation of China (No. 32101470)+3 种基金Foundation (No. 2021KF37) of Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution Control,College of Light Industry and Food Engineering, Guangxi UniversityFoundation of Tianjin Key Laboratory of Pulp & Paper of Tianjin University of Science & Technology (No. 202003, No. 202106)Research Foundation from the University of New BrunswickPost-Doctoral Fellow Programs from Zhejiang Jingxing Paper Co., Ltd
文摘Considering the serious barriers/issues induced by the accumulated starch generated in white water system of old corrugated cardboard(OCC)pulping process,large amounts of accumulated starch in white water would be decomposed by microorganisms and could not be utilized,thereby resulting in severe resource wastage and environmental pollution.This study mainly explored the effects of biodegradation/hydrolysis conditions of the two types of starch substrates(native starch and enzymatically(α-amylase)hydrolyzed starch),which were treated via microorganism degradation within the simulated white water from OCC pulping system and their biodegradation products on the key properties were characterized via X-ray diffraction(XRD),Fourier-transform infrared spectroscopy(FT-IR),and gel permeation chromatography(GPC)technologies.The effects of system temperature,pH value,starch concentration,and biodegradation time on starch biodegradation ratio and the characteristics of obtained biodegradated products from the two types of starches were studied.In addition,the effect ofα-amylase dosage on the biodegradation ratio of enzymatically hydrolyzed starch and its properties was investigated.It was found that the native starch presented a maximal degradation ratio at a system temperature of 55℃and pH value range of 5-7,respectively,the corresponding starch concentration within simulated white water system was 200 mg/L.Whereas the enzymatically hydrolyzed starch exhibited a highest degradation ratio at a system temperature of 50℃and pH value of 5.5,respectively,and the corresponding starch concentration within simulated white water system was 100 mg/L.It was verified that native starch is more readily bio-hydrolyzed and biodegradation-susceptive by microorganisms in simulated white water system of OCC pulping process,while the enzymatically hydrolyzed starch exhibits better biodegradation/hydrolysis resistance to the microbial degradation than that of native starch.This study provides a practical and interesting approach to investigate the starch hydrolysis or biodegradation behaviors in white water system of OCC pulping process,which would greatly contribute to the full recycling and valorized application of starch as a versatile additive during paperboard production.
基金supported by the National Natural Science Foundation of China (No. 22005216 and 52172241)the General Research Fund of Hong Kong (No. CityU 11308321)Tianjin Research Innovation Project for Postgraduate Students (No.2022BKY130)
文摘Suppression of uncontrollable dendrite growth and water-induced side reactions of Zn metal anodes is crucial for achieving long-lasting cycling stability and facilitating the practical implementations of aqueous Zn-metal batteries.To address these challenges,we report in this study a functional nitro-cellulose interfacial layer(NCIL)on the surface of Zn anodes enlightened by a nitro-coordination chemistry strategy.The NCIL exhibits strong zincophilicity and superior coordination capability with Zn^(2+)due to the highly electronegative and highly nucleophilic nature of the nitro functional group.This characteristic facilitates a rapid Zn-ion desolvation process and homogeneous Zn plating,effectively preventing H_(2) evolution and dendrite formation.Additionally,the negatively charged surface of NCIL acts as a shield,repelling SO_(4)^(2-)anions and inhibiting corrosive reactions on the Zn surface.Remarkably,reversible and stable Zn plating/stripping is achieved for over 5100 h at a current density of 1 mA cm^(-2),which is nearly 30 times longer than that of bare Zn anodes.Furthermore,the Zn/V_(2)O_(5) full cells with the functional interface layer deliver a high-capacity retention of 80.3%for over 10,000 cycles at 5 A g^(-1).This research offers valuable insights for the rational development of advanced protective interface layers in order to achieve ultra-long-lifeZnmetal batteries.
基金supported by the National Natural Science Foundation of China(52203066,22005216,51973157,61904123)the Tianjin Natural Science Foundation(18JCQNJC02900)+5 种基金National innovation and entrepreneurship training program for college students(202310058007)Tianjin Municipal college students’innovation and entrepreneurship training program(202310058088)Tianjin Enterprise Science and Technology Commissioner Project(23YDTPJC00490)China Postdoctoral Science Foundation Grant(2023M742135)State Key Laboratory of Membrane and Membrane Separation,Tiangong Universitysupported as part of the opening fund of Key Laboratory of Rare Earths,Chinese Academy of Sciences.
文摘The low ionic conductivities,poor high-voltage stabilities,and lithium dendrite formation of polymer solid electrolytes preclude their use in all-solid-state lithium metal batteries(ASSLMBs).This work provides a simple and scalable technique for constructing fast ion conductor nanofibers(FICNFs)and poly-m-phenyleneisophthalamide(PMIA)nanofibers synergistically enhanced polyethylene oxide(PEO)-based composite solid electrolytes(CSEs)for ASSLMBs.The FICNFs,which were mainly composed of high loadings of ZrO_(2)or Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)nanoparticles,had a percolated ceramic phase inside the nanofibers,while the exposed nanoparticles formed continuous organic–inorganic interfaces with the PEO matrix to enable Li+transport.The interfacial transport rate between ZrO_(2)and PEO was calculated as 4.78×10^(–5)cm^(2)s^(−1)with ab initio molecular dynamics(AIMD)simulations.Besides,the PMIA nanofibers provided strong skeletal support for the CSEs,ensuring excellent mechanical strength and safety for thin CSEs even at high temperatures.More importantly,the amide groups in PMIA provided abundant hydrogen bonds with TFSI−,which lowered the lowest unoccupied molecular orbital(LUMO)level of lithium salts,thus promoting the generation of lithium fluoride-rich solid electrolyte interphase.Consequently,the modified CSEs exhibited satisfactory ionic conductivities(5.38×10^(–4)S cm^(−1)at 50℃)and notable Li dendrite suppression(>1500 h at 0.3 mAh cm^(−2)).The assembled LiFePO_(4)||Li full cells display ultra-long cycles(>2000 cycles)at 50℃ and 40℃.More strikingly,the LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)||Li cell also can stably run for 500 cycles,and the LiFePO_(4)||Li flexible pouch cells also cycled normally,demonstrating tremendous potential for practical application.
基金support of the Natural Science Foundation of Tianjin for Distinguished Young Scholar(No.20JCJQJC00150)Basic Research Program of Jiangsu Province(No.BK20241845)+2 种基金the National Natural Science Foundation of China(No.21872104)Tianjin Research Innovation Project for Postgraduate Students(No.2022BKY135)the National Key Research and Development Program of China(Nos.2020YFA0211003 and 2020YFA0211002).
文摘The advancement of direct seawater electrolysis is a significant step towards sustainable hydrogen production,addressing the critical need for renewable energy sources and efficient resource utilization.However,direct seawater electrolysis has to face several challenges posed by the corrosiveness of highly concentrated chloride and the competitive chlorine evolution reaction(ClER).To overcome these issues,we designed a novel NiP_(2)@CoP electrocatalyst on a porous titanium microfiltration(Ti MF)membrane.The obtained bifunctional NiP_(2)@CoP catalyst outperforms the Pt/C and IrO_(2),as evidenced by its low overpotentials of 192 and 425 mV at a current density of 500 mA·cm^(-2) for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in alkaline seawater(1 M KOH+0.5 M NaCl),respectively.Especially,only 231 and 569 mV overpotentials are required at the current density of 1500 mA·cm^(-2) towards HER and OER in alkaline seawater,respectively.More importantly,no ClER was observed,demonstrating its excellent selectivity to OER.The selection of porous Ti MF membrane as an electrode substrate further enhances the performance by providing a robust structure that promotes the fast generation and release of gas bubbles.Our promising outcomes obtained with NiP_(2)@CoP catalysts on Ti MF support,therefore,pave the way for the commercial viability of direct seawater electrolysis technologies at industrial-level current densities.
基金financially supported by the National Natural Science Foundation of China (Nos. 51973097 and 52173021)the Open Fund of State Key Laboratory of Biobased Fiber Manufacturing Technology (No. SKL202207)
文摘Polyglycolide (PGA) fibers applied as surgical sutures strongly depend on their microstructure. The structural evolution of PGA nascent fibers during single low-temperature stretching and segmented high-temperature stretching was analyzed based on a combination of in situ WAXD/SAXS and DSC measurements. The results indicated that the hot stretching was conducive to the crystal perfection and the local fragmentation and recrystallization of the lamellar crystals may occur under stress induction. The single low-temperature stretching of PGA nascent fibers could be divided into three stages: the stretching of amorphous regions, stretch-induced crystallization and the stretching of crystalline regions. The elongation at break of the fibers can be substantially increased by adopting a segmented stretching method, and the high-temperature stretching can also significantly increase the crystallinity and orientation. The amorphous orientation peak appearing in the low-temperature stretching was gradually converted to crystallization peak during the heating process, which greatly improved the crystallinity and orientation of the fibers. High-temperature stretching compared with low-temperature stretching was more favorable for crystal perfection and structural evolution, where lamellar crystals underwent stress-induced fragmentation recrystallization to transform to fibrous crystals as the strain increased.
基金supported by the National Natural Science Foundation of China(Nos.51908408,21872104)Natural Science Foundation of Tianjin for Distinguished Young Scholar,China(No.20JCJQJC00150)。
文摘The electrochemical oxidation of 5-hydroxymethylfurfural(HMF)to valuable chemicals is an efficient way to upgrade biomass molecules and replace traditional catalytic synthesis.It is crucial to develop efficient and low-cost earth-abundant electrocatalysts to enhance catalytic performance of HMF oxidation.Herein,a new type of two-dimensional(2D)hybrid arrays consisting of Ni Fe layered double hydroxides(LDH)nanosheets and bimetallic sulfide(Ni Fe S)is constructed via interface engineering for efficient electrocatalytic oxidation of HMF to 2,5-furandicarboxylic acid(FDCA).The preparation process of 2D Ni Fe LDH/NiFeS with ultrathin heterostructure involves in anchoring a Co-based metal-organic framework(Co MOF)as template onto the carbon cloth(CC)via in-situ growth,formation of NiFe LDH on the surface of Co MOF and subsequent partial sulfidation.The electrocatalyst of Ni Fe LDH/Ni Fe S exhibits outstanding performance towards HMF oxidation,about 98.5%yield for FDCA and 97.2%Faraday efficiency(FE)in the alkaline electrolyte with 10 mmol/L HMF,as well as excellent stability retaining 90.1%FE for FDCA after six cycles test.Moreover,even at an HMF concentration of 100 mmol/L,the yield and FE for FDCA remain high at 83.6%and 93.6%,respectively.These findings highlight that 2D heterostructure containing abundant interfaces between Ni Fe LDH nanosheets and Ni Fe S can enhance the intrinsic activity of LDH and thus promote the oxidation reaction kinetics.Additionally,the synergistic effect of the bimetallic Ni Fe compounds also improved the selectivity of HMF conversion to FDCA.Our present work demonstrates that constructing 2D ultrathin heterostructure of Ni Fe LDH/Ni Fe S is a facile strategy via interface engineering to enhance the intrinsic activity of LDH electrocatalysts,which would open new avenues toward low-cost and advanced 2D nanocatalysts for sustainable energy conversion and electrochemical valorization of biomass derivatives.
基金National Natural Science Foundation of China,Grant/Award Number:32301530Tianjin Excellent Special Commissioner for Agricultural Science and Technology Project,Grant/Award Number:22ZYCGSN00350Tianjin Enterprise Technology Commissioner Project,Grant/Award Number:22YDTPJC00930。
文摘Supercapacitors exhibit considerable potential as energy storage devices due to their high power density,fast charging and discharging abilities,long cycle life,and ecofriendliness.With the increasing environmental concerns associated with synthetic compounds,the use of environment friendly biopolymers to replace conventional petroleum-based materials has been widely studied.Biomass-based materials are biodegradable,renewable,environment friendly and non-toxic.The unique hierarchical nanostructure,excellent mechanical properties and hydrophilicity allow them to be used to create functional conductive materials with precisely controlled structures and different properties.In this review,the latest development of biomass-based supercapacitor materials is reviewed and discussed.This paper describes the physical and chemical properties of various biopolymers and their impact on supercapacitors,as well as the classification and basic principles of supercapacitors.Then,a comprehensive discussion is presented on the utilization of biomass-based materials in supercapacitors and their recent applications across a range of supercapacitor devices.Finally,an overview of the future prospects and challenges pertaining to the utilization of biomass-based materials in supercapacitors is provided.
