Gel-based flexible wearable sensors have attracted considerable interest in aquatic environments.However,the development of underwater conductive gel sensors with outstanding anti-swelling,mechanical,and sensing capab...Gel-based flexible wearable sensors have attracted considerable interest in aquatic environments.However,the development of underwater conductive gel sensors with outstanding anti-swelling,mechanical,and sensing capabilities faces significant challenges.The aim of this study is to develop anti-swelling and conductive zwitterionic gels and investigate their applications in wireless underwater strain sensing.Multi-functional zwitterionic gels were fabricated by copolymerizing[2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide(SBMA)and acrylic acid(AA)in a mixed solution of aluminum chloride(AlCl3)and poly(vinyl alcohol)(PVA)under ultraviolet light(360 nm).PSBMA was switched from a neutral polymer to a positively charged polymer because of the combination of Al^(3+)with the negative groups SO_(3)^(−).The water molecules were eliminated because of electrostatic repulsion.The gels exhibited anti-swelling properties(swelling ratio<11%),high stretchability(600%strain),and toughness(2451 kJ/m^(3)).The PPAS-Al^(3+)gel was integrated with a wireless Bluetooth system to construct underwater wearable strain sensors that could accurately capture the signals caused by human joint movements and speech recognition even in water.Antibacterial activity(>98.9%inhibition)and stable wireless sensing have potential applications in the fields of wearable sensors,underwater communication,and intelligent healthcare.展开更多
Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.H...Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.Herein,we propose a self-assembly chemical strategy into the LCHEs induced by ordered nanostructure of zwitterionic co-solutes for highly efficient and ultrastable zinc(Zn)metal batteries.Through the systematic screening of six zwitterionic compounds,3-(decyldimethylammonio)propanesulfonate salt(C_(10))with the decyl chain and zwitterions was determined as an optimum to construct quasi-spherical aggregates with a periodic length of 3.77 nm,as confirmed by comprehensive synchronous small-angle X-ray scattering,Guinier,pair distance distribution function,Porod,and other spectroscopic characterizations and molecular dynamic simulation.In particularly,this self-assembled structure in electrolyte environments was attributed to increasing the proportion of both contact and aggregated ion pairs for the formation of LHCEs as well as to providing fast and selective Zn^(2+)conducting channels and uniform solid electrolyte interfaces for facilitated charge transfer kinetics.Moreover,the preferential adsorption of the self-assembled C_(10)on the Zn(002)surface modulated the electrical double layer to suppress hydrogen evolution and corrosion reactions.Consequently,the Zn‖Zn symmetric cells in Zn(OTf)_(2)/C_(10)electrolytes showed long-term plating/stripping behaviors over 2800 h at 1 mA cm^(-2)and 1 mAh cm^(-2)as well as over 1200 h even at 5 mA cm^(-2)and 5 mAh cm^(-2)with a very high depth of discharge of 42.7%.Furthermore,the ZnllVO_(2)/CNT full cells in Zn(OTf)_(2)/C_(10)electrolytes delivered a record-high capacity of 8.10 mAh cm^(-2)at an ultrahigh cathode mass loading of 50 mg cm^(-2)after 150 cycles.展开更多
Solar-driven interfacial desalination(SID)offers a sustainable route for freshwater production,yet its long-term performance is compromised by salt crystallization and microbial fouling under complex marine conditions...Solar-driven interfacial desalination(SID)offers a sustainable route for freshwater production,yet its long-term performance is compromised by salt crystallization and microbial fouling under complex marine conditions.Zwitterionic polymers offer promising nonfouling capabilities,but current zwitterionic hydrogel-based solar evaporators(HSEs)suffer from inadequate hydration and salt vulnerability.Inspired by the natural marine environmental adaptive characteristics of saltwater fish,we report a superhydrated zwitterionic poly(trimethylamine N-oxide,PTMAO)/polyacrylamide(PAAm)/polypyrrole(PPy)hydrogel(PTAP)with dedicated water channels for efficient,durable,and nonfouling SID.The directly linked N⁺and O⁻groups in PTMAO establish a robust hydration shell that facilitates rapid water transport while resisting salt and microbial adhesion.Integrated PAAm and PPy networks enhance mechanical strength and photothermal conversion.PTAP achieves a high evaporation rate of 2.35 kg m^(−2)h^(−1)under 1 kW m^(–2)in 10 wt%NaCl solution,maintaining stable operation over 100 h without salt accumulation.Furthermore,PTAP effectively resists various foulants including proteins,bacterial,and algal adhesion.Molecular dynamics simulations reveal that the exceptional hydration capacity supports its nonfouling properties.This work advances the development of nonfouling HSEs for sustainable solar desalination in real-world marine environments.展开更多
The sluggish Li^(+)migration kinetics and unstable electrode/electrolyte interface severely hinder the commercial application of high-performance lithium metal batteries(LMBs).Herein,an artificial protective layer is ...The sluggish Li^(+)migration kinetics and unstable electrode/electrolyte interface severely hinder the commercial application of high-performance lithium metal batteries(LMBs).Herein,an artificial protective layer is constructed using zwitterionic covalent organic framework(Z-COF)simultaneously containing sulfonate and ethidium groups,aiming to facilitate rapid,uniform Li^(+)transport and stabilize anode interface.The sulfonate groups with high lithiophilicity provide abundant hopping sites for fast Li^(+)diffusion.The ethidium cations immobilize TFSI-and solvent molecules by ion-dipole interactions,which accelerate the dissociation of LiTFSI and Li^(+)desolvation.Moreover,the monodispersed zwitterionic units coupling with ordered micropore structures in Z-COF create exclusive Li^(+)migration channels,modulate homogeneous space charge distribution,kinetically facilitating uniform Li^(+)deposition.Experiments and theoretical calculations indicate that C-F and S-N bonds of TFSI-exhibit enhanced cleavage susceptibility driven by electrostatic attraction,realizing a LiF/Li_(3)N-rich electrolyte/electrode interface.The designed Z-COF protection layer enables Li|Li symmetrical cells stable cycling over 6300 h at 2 mA cm^(-2)/2 mAh cm^(-2).The Z-COF@Li|LiFePO_(4)(LFP)full cells deliver high-capacity retention of 85.2%after 1000 cycles at 8 C.The assembled Z-COF@Li|LFP pouch cells demonstrate a lifespan of more than 240 cycles.This work provides fresh insights into the practical application of zwitterionic COF in next-generation LMBs.展开更多
Flexible strain sensors have received tremendous attention because of their potential applications as wearable sensing devices.However, the integration of key functions into a single sensor, such as high stretchabilit...Flexible strain sensors have received tremendous attention because of their potential applications as wearable sensing devices.However, the integration of key functions into a single sensor, such as high stretchability, low hysteresis, self-adhesion, andexcellent antifreezing performance, remains an unmet challenge. In this respect, zwitterionic hydrogels have emerged asideal material candidates for breaking through the above dilemma. The mechanical properties of most reported zwitterionichydrogels, however, are relatively poor, significantly restricting their use under load-bearing conditions. Traditional improve-ment approaches often involve complex preparation processes, making large-scale production challenging. Additionally,zwitterionic hydrogels prepared with chemical crosslinkers are typically fragile and prone to irreversible deformation underlarge strains, resulting in the slow recovery of structure and function. To fundamentally enhance the mechanical properties ofpure zwitterionic hydrogels, the most effective approach is the regulation of the chemical structure of zwitterionic monomersthrough a targeted design strategy. This study employed a novel zwitterionic monomer carboxybetaine urethane acrylate(CBUTA), which contained one urethane group and one carboxybetaine group on its side chain. Through the direct polym-erization of ultrahigh concentration monomer solutions without adding any chemical crosslinker, we successfully developedpure zwitterionic supramolecular hydrogels with significantly enhanced mechanical properties, self-adhesive behavior, andantifreezing performance. Most importantly, the resultant zwitterionic hydrogels exhibited high tensile strength and tough-ness and displayed ultralow hysteresis under strain conditions up to 1100%. This outstanding performance was attributedto the unique liquid–liquid phase separation phenomenon induced by the ultrahigh concentration of CBUTA monomers inan aqueous solution, as well as the enhanced polymer chain entanglement and the strong hydrogen bonds between urethanegroups on the side chains. The potential application of hydrogels in strain sensors and high-performance triboelectric nano-generators was further explored. Overall, this work provides a promising strategy for developing pure zwitterionic hydrogelsfor flexible strain sensors and self-powered electronic devices.展开更多
Developing advanced ion-conductive networks is crucial for anion exchange membranes(AEMs).A flexible molecular structure facilitates the formation of ion clusters,resulting in enhanced ionic conductivity.Polyacrylates...Developing advanced ion-conductive networks is crucial for anion exchange membranes(AEMs).A flexible molecular structure facilitates the formation of ion clusters,resulting in enhanced ionic conductivity.Polyacrylates,known for their outstanding flexibility and chemical stability,hold significant potential as polymer electrolyte membranes.In this work,we innovatively constructed a series of polyacrylate-based AEMs decorated with pendant zwitterions(designated as PSBPA-X,BSBPA-X,where X=20,30,40).Specifically,the spacer length between the zwitterions is strategically optimized to enhance the ionic conductivity.Atomic force microscopy reveals that a longer spacer length between the zwitterions promotes the microphase separation and the formation of advanced water channels,which facilitates the OH^(-)transport in the BSBPA-40 membrane.Moreover,the stronger electrostatic potential and lower interaction energy between the BSBPA-40 and OH^(-)further contribute to efficient OH^(-)hopping transmission.Consequently,the BSBPA-40 membrane demonstrates the highest OH^(-)conductivity,achieving 102.1 mS cm^(-1)at 80℃ and 90% relative humidity,significantly surpassing that of the PSBPA-40 membrane(75.2 mS cm^(-1)).Additionally,the BSBPA-40 membrane exhibits remarkable flexibility with an improved breaking elongation of 480.5%due to the ionic cross-linking between the zwitterions.Notably,the BSBPA-40 membrane-based zinc-air battery achieves an outstanding power density of 156.7 mW cm^(-2)at room temperature,while its water electrolysis performance reaches 2.1 A cm^(-2)at 2.0 V.These results indicate that the developed membranes hold great promise for applications in sustainable and clean energy technologies.展开更多
Zwitterions(ZIs)are considered as an ideal,novel ionic conductive medium due to their high dipole moment and good solubility of lithium salts.However,the strong interactions between ZIs and Li^(+)severely hinder Li^(+...Zwitterions(ZIs)are considered as an ideal,novel ionic conductive medium due to their high dipole moment and good solubility of lithium salts.However,the strong interactions between ZIs and Li^(+)severely hinder Li^(+)migration.Herein,a quasi-solid electrolyte(MSQSE-2Na)was fabricated by adding sodium bis(fluorosulfonyl)imide(NaFSI)to sulfobetaine methacrylate(SBMA,a ZI)based polymerization system.Na^(+)occupies the–SO_(3)^(-)site in SBMA prior to Li^(+),which weakens the self-crosslinking of SBMA and frees the Li^(+)bound to the polymer segments.Thus,the polymer conformation of MSQSE-2Na changes to a relaxed,homogeneous"sea-island"type.Meanwhile,Na^(+),due to its electron-withdrawing effect,decreases the electron cloud density of the polymer segments,building a weakly coordinated environment in MSQSE-2Na.Consequently,MSQSE-2Na exhibits excellent ionic conductivity of 7.38×10^(-4)S cm^(-1)and a high Li^(+)transference number of 0.632 at 25℃.The(-)Li|MSQSE-2Na|Li(+)cells exhibit super stability,sustaining operation for over 6182h.The(-)Li|MSQSE-2Na|LiFePO_(4)(+)cells demonstrate outstanding charge/discharge reversibility with a Coulombic efficiency exceeding 99.9%over 270 cycles(≈4500 h),with a capacity retention of 70.0%.This work proposes a new design concept for regulating the polymer conformation and charge characteristics through competitive coordination,thereby advancing the application of ZI-based polymer electrolytes in lithium metal batteries.展开更多
Traditional hydrogels are inevitably damaged during practical applications,resulting in a gradual deterioration of their functional efficacy.A primary strategy to address this issue involves developing hydrogels with ...Traditional hydrogels are inevitably damaged during practical applications,resulting in a gradual deterioration of their functional efficacy.A primary strategy to address this issue involves developing hydrogels with inherent self-healing properties.In this study,we report the synthesis of self-healing polyacrylate hydrogels that integrate zwitterions,hydrophilic nano-silica and aluminum ions.Due to the synergistic effect of multiple hydrogen bonds,coordination bonds and electrostatic interactions,the tensile strength of the hydrogel is enhanced from 15.1 to 162.6 kPa.Moreover,the electrical resistance and tensile strength of the hydrogel can almost recover to its initial values after 20 min of healing at room temperature,exhibiting remarkable self-healing performance.Furthermore,the zwitterionic polyacrylate hydrogel serves as a wearable sensor with the capability of accurately response to the bending and stretching of human joints,exhibting a gauge factor of 1.87 under tensile strain ranging from 80% to 100%.Even after being freezed at-20℃ for 3 h,the zwitterionic polyacrylate hydrogel retains its exceptional writing performance.In conclusion,the hydrogels developed in this study demonstrate significant potential for wearable electronics applications.展开更多
Zwitterionic materials with covalently tethered cations and anions have great potential as electrolyte additives for aqueous Znion batteries(AZIBs)owing to their appealing intrinsic characteristics and merits.However,...Zwitterionic materials with covalently tethered cations and anions have great potential as electrolyte additives for aqueous Znion batteries(AZIBs)owing to their appealing intrinsic characteristics and merits.However,the impact of cationic and anionic moieties within zwitterions on enhancing the performance of AZIBs remains poorly understood.Herein,three zwitterions,namely carboxybetaine methacrylate(CBMA),sulfobetaine methacrylate(SBMA),and 2-methacryloyloxyethyl phosphorylcholine(MPC),were selected as additives to investigate their different action mechanisms in AZIBs.All three zwitterions have the same quaternary ammonium as the positively charged group,but having different negatively charged segments,i.e.,carboxylate,sulfonate,and phosphate for CBMA,SBMA,and MPC,respectively.By systematical electrochemical analysis,these zwitterions all contribute to enhanced cycling life of Zn anode,with MPC having the most pronounced effect,which can be attributed to the synergistic effect of positively quaternary ammonium group and unique negatively phosphate groups.As a result,the Zn//Zn cell with MPC as additive in ZnSO_(4)electrolyte exhibits an ultralong lifespan over 5000 h.This work proposes new insights to the future development of multifunctional zwitterionic additives for remarkably stable AZIBs.展开更多
Orthodontic appliances are essential for dentofacial deformity corrections.However,orthodontic appliances inadvertently increase the risk of bacterial colonization and dental calculus formation,which may lead to denta...Orthodontic appliances are essential for dentofacial deformity corrections.However,orthodontic appliances inadvertently increase the risk of bacterial colonization and dental calculus formation,which may lead to dental caries and gingivitis.Herein,this study developed a pH-responsive antifouling coating by integrating a zwitterionic hydrogel(ZH)with pH-responsive microcapsules(PRMs)encapsulating bactericide,displaying excellent synergies of anti-bacteria and anti-calculus for orthodontic appliances.The excellent antifouling properties can be attributed to two following points:ZH provides anti-adhesion properties via electrostatically induced hydration layers,while the PRMs can kill bacteria by on-demand bactericide release under acidic conditions.Results demonstrated that ZH+PRMs coating significantly reduced bacterial adhesion and inhibited calculus formation while maintaining excellent biocompatibility.By optimizing PRMs concentrations(0–15 wt%),compared with ZH,the antibacterial efficiency of ZH+PRMs(optimal concentration 10 wt%)increased from 49.8%±7.3%to 95.2%±1.1%for E.coli and from 85.7%±3.5%to 91.3%±1.4%for S.mutans.Compared with pristine steel(SS),ZH+PRMs coating showed ca.97.0%reduction for calcium carbonate and ca.87.3%reduction for calcium phosphate.In an in vitro model,compared with SS,our coating extended the crystal biofilm inhibition effect from one day to five days.Therefore,this study can provide promising strategies for reducing the risk of dental caries and gingivitis during orthodontic treatment.展开更多
基金financially supported by the Fundamental Research Program of the Shanxi Province(No.202203021211023).
文摘Gel-based flexible wearable sensors have attracted considerable interest in aquatic environments.However,the development of underwater conductive gel sensors with outstanding anti-swelling,mechanical,and sensing capabilities faces significant challenges.The aim of this study is to develop anti-swelling and conductive zwitterionic gels and investigate their applications in wireless underwater strain sensing.Multi-functional zwitterionic gels were fabricated by copolymerizing[2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide(SBMA)and acrylic acid(AA)in a mixed solution of aluminum chloride(AlCl3)and poly(vinyl alcohol)(PVA)under ultraviolet light(360 nm).PSBMA was switched from a neutral polymer to a positively charged polymer because of the combination of Al^(3+)with the negative groups SO_(3)^(−).The water molecules were eliminated because of electrostatic repulsion.The gels exhibited anti-swelling properties(swelling ratio<11%),high stretchability(600%strain),and toughness(2451 kJ/m^(3)).The PPAS-Al^(3+)gel was integrated with a wireless Bluetooth system to construct underwater wearable strain sensors that could accurately capture the signals caused by human joint movements and speech recognition even in water.Antibacterial activity(>98.9%inhibition)and stable wireless sensing have potential applications in the fields of wearable sensors,underwater communication,and intelligent healthcare.
基金financially supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.NRF-2020R1A3B2079803 and No.RS-2024-00453815),Republic of Korea。
文摘Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.Herein,we propose a self-assembly chemical strategy into the LCHEs induced by ordered nanostructure of zwitterionic co-solutes for highly efficient and ultrastable zinc(Zn)metal batteries.Through the systematic screening of six zwitterionic compounds,3-(decyldimethylammonio)propanesulfonate salt(C_(10))with the decyl chain and zwitterions was determined as an optimum to construct quasi-spherical aggregates with a periodic length of 3.77 nm,as confirmed by comprehensive synchronous small-angle X-ray scattering,Guinier,pair distance distribution function,Porod,and other spectroscopic characterizations and molecular dynamic simulation.In particularly,this self-assembled structure in electrolyte environments was attributed to increasing the proportion of both contact and aggregated ion pairs for the formation of LHCEs as well as to providing fast and selective Zn^(2+)conducting channels and uniform solid electrolyte interfaces for facilitated charge transfer kinetics.Moreover,the preferential adsorption of the self-assembled C_(10)on the Zn(002)surface modulated the electrical double layer to suppress hydrogen evolution and corrosion reactions.Consequently,the Zn‖Zn symmetric cells in Zn(OTf)_(2)/C_(10)electrolytes showed long-term plating/stripping behaviors over 2800 h at 1 mA cm^(-2)and 1 mAh cm^(-2)as well as over 1200 h even at 5 mA cm^(-2)and 5 mAh cm^(-2)with a very high depth of discharge of 42.7%.Furthermore,the ZnllVO_(2)/CNT full cells in Zn(OTf)_(2)/C_(10)electrolytes delivered a record-high capacity of 8.10 mAh cm^(-2)at an ultrahigh cathode mass loading of 50 mg cm^(-2)after 150 cycles.
基金supported by National Natural Science Foundation of China(22209036,U23A20119)Hebei Provincial Natural Science Foundation,Excellent Youth Project(E2023202069)+1 种基金National Key R&D Program of China(2024YFF0506000,2024YFB4609100)Fundamental Research Foundation from Hebei University of Technology(424132016,282021485).
文摘Solar-driven interfacial desalination(SID)offers a sustainable route for freshwater production,yet its long-term performance is compromised by salt crystallization and microbial fouling under complex marine conditions.Zwitterionic polymers offer promising nonfouling capabilities,but current zwitterionic hydrogel-based solar evaporators(HSEs)suffer from inadequate hydration and salt vulnerability.Inspired by the natural marine environmental adaptive characteristics of saltwater fish,we report a superhydrated zwitterionic poly(trimethylamine N-oxide,PTMAO)/polyacrylamide(PAAm)/polypyrrole(PPy)hydrogel(PTAP)with dedicated water channels for efficient,durable,and nonfouling SID.The directly linked N⁺and O⁻groups in PTMAO establish a robust hydration shell that facilitates rapid water transport while resisting salt and microbial adhesion.Integrated PAAm and PPy networks enhance mechanical strength and photothermal conversion.PTAP achieves a high evaporation rate of 2.35 kg m^(−2)h^(−1)under 1 kW m^(–2)in 10 wt%NaCl solution,maintaining stable operation over 100 h without salt accumulation.Furthermore,PTAP effectively resists various foulants including proteins,bacterial,and algal adhesion.Molecular dynamics simulations reveal that the exceptional hydration capacity supports its nonfouling properties.This work advances the development of nonfouling HSEs for sustainable solar desalination in real-world marine environments.
基金supported by the National Natural Science Foundation of China(52472093,52176185)the Department of Science and Technology of Hubei Province of China(2022CFA069,2022BAA086).
文摘The sluggish Li^(+)migration kinetics and unstable electrode/electrolyte interface severely hinder the commercial application of high-performance lithium metal batteries(LMBs).Herein,an artificial protective layer is constructed using zwitterionic covalent organic framework(Z-COF)simultaneously containing sulfonate and ethidium groups,aiming to facilitate rapid,uniform Li^(+)transport and stabilize anode interface.The sulfonate groups with high lithiophilicity provide abundant hopping sites for fast Li^(+)diffusion.The ethidium cations immobilize TFSI-and solvent molecules by ion-dipole interactions,which accelerate the dissociation of LiTFSI and Li^(+)desolvation.Moreover,the monodispersed zwitterionic units coupling with ordered micropore structures in Z-COF create exclusive Li^(+)migration channels,modulate homogeneous space charge distribution,kinetically facilitating uniform Li^(+)deposition.Experiments and theoretical calculations indicate that C-F and S-N bonds of TFSI-exhibit enhanced cleavage susceptibility driven by electrostatic attraction,realizing a LiF/Li_(3)N-rich electrolyte/electrode interface.The designed Z-COF protection layer enables Li|Li symmetrical cells stable cycling over 6300 h at 2 mA cm^(-2)/2 mAh cm^(-2).The Z-COF@Li|LiFePO_(4)(LFP)full cells deliver high-capacity retention of 85.2%after 1000 cycles at 8 C.The assembled Z-COF@Li|LFP pouch cells demonstrate a lifespan of more than 240 cycles.This work provides fresh insights into the practical application of zwitterionic COF in next-generation LMBs.
基金supported by the National Natural Science Foundation of China(Nos.T2222013 and 52073203)Tianjin Natural Science Foundation(No.22JCQNJC01040)the State Key Laboratory of Molecular Engineering of Polymers(Fudan University)(No.K2024-19).
文摘Flexible strain sensors have received tremendous attention because of their potential applications as wearable sensing devices.However, the integration of key functions into a single sensor, such as high stretchability, low hysteresis, self-adhesion, andexcellent antifreezing performance, remains an unmet challenge. In this respect, zwitterionic hydrogels have emerged asideal material candidates for breaking through the above dilemma. The mechanical properties of most reported zwitterionichydrogels, however, are relatively poor, significantly restricting their use under load-bearing conditions. Traditional improve-ment approaches often involve complex preparation processes, making large-scale production challenging. Additionally,zwitterionic hydrogels prepared with chemical crosslinkers are typically fragile and prone to irreversible deformation underlarge strains, resulting in the slow recovery of structure and function. To fundamentally enhance the mechanical properties ofpure zwitterionic hydrogels, the most effective approach is the regulation of the chemical structure of zwitterionic monomersthrough a targeted design strategy. This study employed a novel zwitterionic monomer carboxybetaine urethane acrylate(CBUTA), which contained one urethane group and one carboxybetaine group on its side chain. Through the direct polym-erization of ultrahigh concentration monomer solutions without adding any chemical crosslinker, we successfully developedpure zwitterionic supramolecular hydrogels with significantly enhanced mechanical properties, self-adhesive behavior, andantifreezing performance. Most importantly, the resultant zwitterionic hydrogels exhibited high tensile strength and tough-ness and displayed ultralow hysteresis under strain conditions up to 1100%. This outstanding performance was attributedto the unique liquid–liquid phase separation phenomenon induced by the ultrahigh concentration of CBUTA monomers inan aqueous solution, as well as the enhanced polymer chain entanglement and the strong hydrogen bonds between urethanegroups on the side chains. The potential application of hydrogels in strain sensors and high-performance triboelectric nano-generators was further explored. Overall, this work provides a promising strategy for developing pure zwitterionic hydrogelsfor flexible strain sensors and self-powered electronic devices.
基金financially supported by the National Key Research and Development Program of China(2022YFE0138900)the National Natural Science Foundation of China(21972017)the“Scientific and Technical Innovation Action Plan”Basic Research Field of Shanghai Science and Technology Committee(19JC1410500).
文摘Developing advanced ion-conductive networks is crucial for anion exchange membranes(AEMs).A flexible molecular structure facilitates the formation of ion clusters,resulting in enhanced ionic conductivity.Polyacrylates,known for their outstanding flexibility and chemical stability,hold significant potential as polymer electrolyte membranes.In this work,we innovatively constructed a series of polyacrylate-based AEMs decorated with pendant zwitterions(designated as PSBPA-X,BSBPA-X,where X=20,30,40).Specifically,the spacer length between the zwitterions is strategically optimized to enhance the ionic conductivity.Atomic force microscopy reveals that a longer spacer length between the zwitterions promotes the microphase separation and the formation of advanced water channels,which facilitates the OH^(-)transport in the BSBPA-40 membrane.Moreover,the stronger electrostatic potential and lower interaction energy between the BSBPA-40 and OH^(-)further contribute to efficient OH^(-)hopping transmission.Consequently,the BSBPA-40 membrane demonstrates the highest OH^(-)conductivity,achieving 102.1 mS cm^(-1)at 80℃ and 90% relative humidity,significantly surpassing that of the PSBPA-40 membrane(75.2 mS cm^(-1)).Additionally,the BSBPA-40 membrane exhibits remarkable flexibility with an improved breaking elongation of 480.5%due to the ionic cross-linking between the zwitterions.Notably,the BSBPA-40 membrane-based zinc-air battery achieves an outstanding power density of 156.7 mW cm^(-2)at room temperature,while its water electrolysis performance reaches 2.1 A cm^(-2)at 2.0 V.These results indicate that the developed membranes hold great promise for applications in sustainable and clean energy technologies.
基金supported by the National Natural Science Foundation of China(22078228)。
文摘Zwitterions(ZIs)are considered as an ideal,novel ionic conductive medium due to their high dipole moment and good solubility of lithium salts.However,the strong interactions between ZIs and Li^(+)severely hinder Li^(+)migration.Herein,a quasi-solid electrolyte(MSQSE-2Na)was fabricated by adding sodium bis(fluorosulfonyl)imide(NaFSI)to sulfobetaine methacrylate(SBMA,a ZI)based polymerization system.Na^(+)occupies the–SO_(3)^(-)site in SBMA prior to Li^(+),which weakens the self-crosslinking of SBMA and frees the Li^(+)bound to the polymer segments.Thus,the polymer conformation of MSQSE-2Na changes to a relaxed,homogeneous"sea-island"type.Meanwhile,Na^(+),due to its electron-withdrawing effect,decreases the electron cloud density of the polymer segments,building a weakly coordinated environment in MSQSE-2Na.Consequently,MSQSE-2Na exhibits excellent ionic conductivity of 7.38×10^(-4)S cm^(-1)and a high Li^(+)transference number of 0.632 at 25℃.The(-)Li|MSQSE-2Na|Li(+)cells exhibit super stability,sustaining operation for over 6182h.The(-)Li|MSQSE-2Na|LiFePO_(4)(+)cells demonstrate outstanding charge/discharge reversibility with a Coulombic efficiency exceeding 99.9%over 270 cycles(≈4500 h),with a capacity retention of 70.0%.This work proposes a new design concept for regulating the polymer conformation and charge characteristics through competitive coordination,thereby advancing the application of ZI-based polymer electrolytes in lithium metal batteries.
基金financially supported by the National Key Research and Development Program of China(2022YFE0138900)the National Natural Science Foundation of China(21972017)+1 种基金the Fundamental Research Funds for the Central Universities of Ministry of Education of China(D5000240188)the"Scientific and Technical Innovation Action Plan"Basic Research Field of Shanghai Science and Technology Committee(19JC1410500)。
文摘Traditional hydrogels are inevitably damaged during practical applications,resulting in a gradual deterioration of their functional efficacy.A primary strategy to address this issue involves developing hydrogels with inherent self-healing properties.In this study,we report the synthesis of self-healing polyacrylate hydrogels that integrate zwitterions,hydrophilic nano-silica and aluminum ions.Due to the synergistic effect of multiple hydrogen bonds,coordination bonds and electrostatic interactions,the tensile strength of the hydrogel is enhanced from 15.1 to 162.6 kPa.Moreover,the electrical resistance and tensile strength of the hydrogel can almost recover to its initial values after 20 min of healing at room temperature,exhibiting remarkable self-healing performance.Furthermore,the zwitterionic polyacrylate hydrogel serves as a wearable sensor with the capability of accurately response to the bending and stretching of human joints,exhibting a gauge factor of 1.87 under tensile strain ranging from 80% to 100%.Even after being freezed at-20℃ for 3 h,the zwitterionic polyacrylate hydrogel retains its exceptional writing performance.In conclusion,the hydrogels developed in this study demonstrate significant potential for wearable electronics applications.
基金supported by the Australian Research Council(LP220100036)the National Key Research and Development Program(2022YFB2502104 and 2022YFA1602700)+3 种基金the Key Research and Development Program of Jiangsu Provincial Department of Science and Technology of China(BE2022332)the Jiangsu Carbon Peak Carbon Neutralization Science and Technology Innovation Special Fund(BE2022605)the Australian Research Council for his Discovery Early Career Researcher Award fellowship(DE230101105)the China Scholarship Council(CSC,grant no.202306190185)for funding a scholarship。
文摘Zwitterionic materials with covalently tethered cations and anions have great potential as electrolyte additives for aqueous Znion batteries(AZIBs)owing to their appealing intrinsic characteristics and merits.However,the impact of cationic and anionic moieties within zwitterions on enhancing the performance of AZIBs remains poorly understood.Herein,three zwitterions,namely carboxybetaine methacrylate(CBMA),sulfobetaine methacrylate(SBMA),and 2-methacryloyloxyethyl phosphorylcholine(MPC),were selected as additives to investigate their different action mechanisms in AZIBs.All three zwitterions have the same quaternary ammonium as the positively charged group,but having different negatively charged segments,i.e.,carboxylate,sulfonate,and phosphate for CBMA,SBMA,and MPC,respectively.By systematical electrochemical analysis,these zwitterions all contribute to enhanced cycling life of Zn anode,with MPC having the most pronounced effect,which can be attributed to the synergistic effect of positively quaternary ammonium group and unique negatively phosphate groups.As a result,the Zn//Zn cell with MPC as additive in ZnSO_(4)electrolyte exhibits an ultralong lifespan over 5000 h.This work proposes new insights to the future development of multifunctional zwitterionic additives for remarkably stable AZIBs.
基金supported by the National Natural Science Foundation of China(Nos.51973003 and 22275203)the Beijing Natural Science Foundation(No.JQ23008)。
文摘Orthodontic appliances are essential for dentofacial deformity corrections.However,orthodontic appliances inadvertently increase the risk of bacterial colonization and dental calculus formation,which may lead to dental caries and gingivitis.Herein,this study developed a pH-responsive antifouling coating by integrating a zwitterionic hydrogel(ZH)with pH-responsive microcapsules(PRMs)encapsulating bactericide,displaying excellent synergies of anti-bacteria and anti-calculus for orthodontic appliances.The excellent antifouling properties can be attributed to two following points:ZH provides anti-adhesion properties via electrostatically induced hydration layers,while the PRMs can kill bacteria by on-demand bactericide release under acidic conditions.Results demonstrated that ZH+PRMs coating significantly reduced bacterial adhesion and inhibited calculus formation while maintaining excellent biocompatibility.By optimizing PRMs concentrations(0–15 wt%),compared with ZH,the antibacterial efficiency of ZH+PRMs(optimal concentration 10 wt%)increased from 49.8%±7.3%to 95.2%±1.1%for E.coli and from 85.7%±3.5%to 91.3%±1.4%for S.mutans.Compared with pristine steel(SS),ZH+PRMs coating showed ca.97.0%reduction for calcium carbonate and ca.87.3%reduction for calcium phosphate.In an in vitro model,compared with SS,our coating extended the crystal biofilm inhibition effect from one day to five days.Therefore,this study can provide promising strategies for reducing the risk of dental caries and gingivitis during orthodontic treatment.
