Aqueous zinc(Zn)-ion batteries hold great promise as renewable energy storage system for carbon-neutral energy transition.However,Zn anodes suffer from poor Zn plating/stripping reversibility due to Zn dendrite growth...Aqueous zinc(Zn)-ion batteries hold great promise as renewable energy storage system for carbon-neutral energy transition.However,Zn anodes suffer from poor Zn plating/stripping reversibility due to Zn dendrite growth and side reactions.Existing Zn interfacial modification strategies based on single-component or homogeneous structure are insufficient to address these issues comprehensively.Herein,we rationally designed an organic-inorganic hybrid interfacial layer with rigid-to-soft graded structure for dendrite-free and stable Zn anodes.A liquid plasma-assisted oxidation technology is developed to rapidly construct a porous ZnO inner framework in situ.This ZnO layer offers high interfacial energy,mechanical robustness,and an open structure that facilitates ion transport while firmly anchoring a subsequently coated soft polymer layer.The resulting architecture presents a structurally graded and functionally complementary interface,enabling effective dendrite suppression,continuous Zn ion transport,and enhanced corrosion resistance.As a result,a long cycling stability of more than 6000 h can be achieved at 1 mA cm^(-2)for 1 mAh cm^(-2)in symmetric cells.When used as anodes for zinc-iodine full battery,the hybrid interlayer can effectively prevent the Zn anodes from the corrosion by polyiodine,enabling stable cycling and negligible capacity decay(~0.02‰per cycle)for over 10,000 cycles at 2.0 A g^(-1).This work demonstrates a promising interfacial design strategy and introduces a novel liquid plasma-assisted oxidation route for fabricating high-performance Zn anodes towards next-generation aqueous batteries.展开更多
Zinc(Zn)deficiency is a global health issue,exacerbated by low Zn concentration and poor bioavailability in rice,primarily due to phytic acid(PA)interference.In this study,four doubled haploid(DH)progenies(DH1,DH11,DH...Zinc(Zn)deficiency is a global health issue,exacerbated by low Zn concentration and poor bioavailability in rice,primarily due to phytic acid(PA)interference.In this study,four doubled haploid(DH)progenies(DH1,DH11,DH18,and DH29)with distinct Zn and PA profiles were used to evaluate the effects of varying degrees of milling(DOM)on Zn bioavailability.Results showed DOM followed a double-exponential decay pattern(R^(2)>0.99)with milling time,varying among the four DH lines under identical milling conditions.As DOM increased,Zn,PA,and phosphorus(P)concentrations decreased progressively.展开更多
Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage,but their commercialization is hindered by zinc anode challenges,notably parasitic reactions and dendrite growth.Herein,we...Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage,but their commercialization is hindered by zinc anode challenges,notably parasitic reactions and dendrite growth.Herein,we present a biodegradable biomass-derived protective layer,primarily composed of curcumin,as a zincophilic interface for AZMBs.The curcumin-based layer,fabricated via a homogeneous solution process,exhibits strong adhesion,uniform coverage,and robust mechanical integrity.Rich polar functional groups in curcumin facilitate homogeneous Zn~(2+)flux and suppress side reactions.The curcumin-based layer shows a favorable affinity for zinc trifluoromethanesulfonate(Zn(OTf)_(2))electrolyte,which is the representative of organic zinc salts,enabling optimal thickness for both protection and ion transport.The protected Zn anodes demonstrate an extended lifespan of 2500 h in symmetrical cells and a high Coulombic efficiency of 99.15%.Furthermore,Zn(OTf)_(2)-based system typically exhibits poor stability at high current densities.Fortunately,the lifespan of symmetrical cells was extended by 40-fold at the high current density.When paired with an Na V_(3)O_(8)·1.5H_(2)O(NVO)cathode,the system achieves 86.5%capacity retention after 3000 cycles at a large specific current density of 10 A g^(-1).These results underscore the efficacy of the curcumin-based protective layer in enhancing the reversibility and stability of metal electrodes,specifically relieving the instability of Zn(OTf)_(2)-based systems at high current densities,advancing its commercial viability.展开更多
Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density...Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.展开更多
Aqueous zinc-ion batteries(AZIBs)are currently confronted with the challenge of achieving long-term cyclic stability under high current densities.This issue is primarily attributed to the excessive growth of dendrites...Aqueous zinc-ion batteries(AZIBs)are currently confronted with the challenge of achieving long-term cyclic stability under high current densities.This issue is primarily attributed to the excessive growth of dendrites and the occurrence of significant side reactions.Herein,sucralose(SCL),as an electrolyte additive,has been used to promote the exposure of the Zn(002)texture.The introduction of SCL can adjust the Zn~(2+)nucleation and diffusion along different crystal facets,promoting the exposure of the Zn(002)texture.By substituting water molecules in the[Zn(H_(2)O)_(6)]~(2+),SCL reconfigures the hydrogen bond network in the electrolyte,reconstructing the solvation structure and suppressing the hydrogen evolution reaction.Consequently,the Zn//Zn symmetric battery exhibits long-term cycling stability of over 4900 h at 1 mA cm^(-2)-1 mAh cm^(-2).Even at a harsh condition of 30 mA cm^(-2)-30 mAh cm^(-2)(DOD=73.3%),it can stably cycle for 171 h.The CE of the Zn//Cu half battery reaches 99.61% at 0.2 mA cm^(-2)with 0.2 mAh cm^(-2).Employing the optimized electrolyte,after 500 cycles,a high specific capacity of 420 mAh g^(-1)can be retained for the NH_4V_4O_(10)//Zn full battery at 500 mA g^(-1),corresponding to a capacity retention of 90.7%.展开更多
Green solvent pretreatment of biomass represents a promising ap-proach for enhancing the econom-ic value of lignocellulosic deriva-tives.In this study,corncob biomass was treated with a diol-based deep eutectic solven...Green solvent pretreatment of biomass represents a promising ap-proach for enhancing the econom-ic value of lignocellulosic deriva-tives.In this study,corncob biomass was treated with a diol-based deep eutectic solvent(DES)under mild conditions,facilitating efficient cellulose separation.The extracted cellulose was subsequently used to fabricate cellulose hydrogels in an aqueous zinc chloride solution.The resulting hydrogel exhibited a“water-in-salt”effect due to the high concentration of ZnCl_(2).Leveraging the antifreeze properties of sorbitol,the system demon-strated outstanding low-temperature electrochemical performance,including a broad operat-ing voltage window and an ionic conductivity of 38.4 mS·cm^(-1)at-20℃.At 20℃,the de-vice achieved an energy density of 206 Wh·kg^(-1)and a power density of 2701.05 W·kg^(-1)at a current density of 1 A·g^(-1).Moreover,the flexible zinc-ion hybrid supercapacitor(ZHSC)maintained 89%of its capacitance and nearly 100%Coulombic efficiency after 5500 cycles at 20℃.This work not only advances the development of zinc-ion energy storage devices but al-so establishes a new paradigm for the green and direct utilization of biomass-derived materi-als.展开更多
Zinc-ion hybrid supercapacitors(ZIHCs)are compelling candidates for next-generation energy storage owing to their intrinsic safety,low cost,and high power density.However,their practical implementation remains hindere...Zinc-ion hybrid supercapacitors(ZIHCs)are compelling candidates for next-generation energy storage owing to their intrinsic safety,low cost,and high power density.However,their practical implementation remains hindered by the limited energy density of traditional carbon-based cathodes.Here,we rationally design porous carbon nanofibers embedded with atomically dispersed Zn and Fe dual-metal sites(ZnFe/PCNFs),synthesized via electrospinning followed by controlled carbonization.The introduction of Fe modulates the local electronic structure of Zn centers,thereby facilitating enhanced d-orbital hybridization and stronger ion adsorption through the formation of ZnFeN_(6) coordination motifs.Coupled with high surface area and hierarchical porosity,these atomic-level interactions facilitate exceptional ion accessibility and rapid charge-transfer kinetics.As a cathode for ZIHCs,ZnFe/PCNFs deliver a specific capacity of 213 mAh g^(-1),exceptional high-rate capability,and longterm cycling stability over 20000 cycles.This work elucidates mechanisms of dual-metal atomic coordination and provides a robust design strategy for high-performance,durable aqueous energy storage systems.展开更多
The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter per...The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.展开更多
Aqueous zinc-ion batteries are regarded as promising electrochemical energy-storage systems for various applications because of their high safety,low costs,and high capacities.However,dendrite formation and side react...Aqueous zinc-ion batteries are regarded as promising electrochemical energy-storage systems for various applications because of their high safety,low costs,and high capacities.However,dendrite formation and side reactions during zinc plating or stripping greatly reduce the capacity and cycle life of a battery and subsequently limit its practical application.To address these issues,we modified the surface of a zinc anode with a functional bilayer composed of zincophilic Cu and flexible polymer layers.The zincophilic Cu interfacial layer was prepared through CuSO_(4)solution pretreatment to serve as a nucleation site to facilitate uniform Zn deposition.Meanwhile,the polymer layer was coated onto the Cu interface layer to serve as a protective layer that would prevent side reactions between zinc and electrolytes.Benefiting from the synergistic effect of the zincophilic Cu and protective polymer layers,the symmetric battery exhibits an impressive cycle life,lasting over 2900 h at a current density of 1 m A·cm^(-2)with a capacity of 1 m A·h·cm^(-2).Moreover,a full battery paired with a vanadium oxide cathode achieves a remarkable capacity retention of 72%even after 500 cycles.展开更多
Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aq...Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aqueous electrolytes.A zincophilic carbon(ZC)layer was deposited on a Zn metal foil at 450°C by the up-stream pyrolysis of a hydrogen-bonded supramolecular substance framework,as-sembled from melamine(ME)and cyanuric acid(CA).The zincophilic groups(C=O and C=N)in the ZC layer guide uniform zinc plating/stripping and eliminate dendrites and side reactions.so that assembled symmetrical batteries(ZC@Zn//ZC@Zn)have a long-term service life of 2500 h at 1 mA cm^(−2) and 1 mAh cm^(−2),which is much longer than that of bare Zn anodes(180 h).In addition,ZC@Zn//V2O5 full batteries have a higher capacity of 174 mAh g^(−1) after 1200 cycles at 2 A g^(−1) than a Zn//V_(2)O_(5) counterpart(100 mAh g^(−1)).The strategy developed for the low-temperat-ure deposition of the ZC layer is a new way to construct advanced zinc metal anodes for ZMBs.展开更多
Zinc(Zn)is an essential micronutrient for both plants and humans.Zn deficiency is common in many paddy fields and reduces yield and grain Zn content(GZC).To accelerate breeding for improved GZC and Zn deficiency toler...Zinc(Zn)is an essential micronutrient for both plants and humans.Zn deficiency is common in many paddy fields and reduces yield and grain Zn content(GZC).To accelerate breeding for improved GZC and Zn deficiency tolerance(ZDT)rice varieties,it is important to identify genes regulating Zn homeostasis.In this study,a member of the Ser/Thr protein phosphatase family,LOC_Os07g48840(named as OsGZ7),was found to contributed to ZDT and GZC in rice.The expression of OsGZ7 in roots and shoots was inhibited by Zn deficiency and toxicity,but induced by iron(Fe),manganese(Mn),and copper(Cu)deficiency,as well as chromium toxicity.OsGZ7 localized to the cytoplasm and was expressed in all tissues during the tillering,flowering,and grain-filling stages,particularly in the leaf blade and leaf sheath.At the seedling stage,knockout of OsGZ7 enhanced ZDT and increased Zn accumulation in both roots and shoots.At the maturity stage,knockout of OsGZ7 enhanced GZC,while overexpression of OsGZ7 reduced GZC.RNA-seq analysis suggested that OsGZ7 might regulate Zn homeostasis by affecting metal binding,hormone signal transduction,and oxidoreductase activity.Taken together,our findings indicate that OsGZ7 contributes to ZDT and Zn accumulation in rice.展开更多
Dendrite growth represents one of the most significant challenges that impede the development of aqueous zinc-ion batteries.Herein,Gd^(3+)ions are introduced into conventional electrolytes as a microlevelling agent to...Dendrite growth represents one of the most significant challenges that impede the development of aqueous zinc-ion batteries.Herein,Gd^(3+)ions are introduced into conventional electrolytes as a microlevelling agent to achieve dendrite-free zinc electrodeposition.Simulation and experimental results demonstrate that these Gd^(3+)ions are preferentially adsorbed onto the zinc surface,which enables dendritefree zinc anodes by activating the microlevelling effect during electrodeposition.In addition,the Gd^(3+)additives effectively inhibit side reactions and facilitate the desolvation of[Zn(H_(2)O)_(6)]^(2+),leading to highly reversible zinc plating/stripping.Due to these improvements,the zinc anode demonstrates a significantly prolonged cycle life of 2100 h and achieves an exceptional average Coulombic efficiency of 99.72%over 1400 cycles.More importantly,the Zn//NH_(4)V_(4)O_(10)full cell shows a high capacity retention rate of 85.6%after 1000 cycles.This work not only broadens the application of metallic cations in battery electrolytes but also provides fundamental insights into their working mechanisms.展开更多
Aqueous zinc-ion batteries(AZIBs)present a promising option for next-generation batteries given their high safety,eco-friendliness,and resource sustainability.Nonetheless,the practical application of zinc anodes is hi...Aqueous zinc-ion batteries(AZIBs)present a promising option for next-generation batteries given their high safety,eco-friendliness,and resource sustainability.Nonetheless,the practical application of zinc anodes is hindered by inevitable parasitic reactions and dendrite growth.Here,zinc alloy layers(i.e.,ZnCo and ZnFe alloys)were rationally constructed on the zinc surface by chemical displacement reactions.The alloying process exposes more(002)planes of the ZnCo anode to guide the preferential and dendrite-free zinc deposition.Furthermore,the ZnCo alloy layer not only effectively inhibits water-induced side reactions but also accelerates electrode kinetics,enabling highly reversible zinc plating/stripping.As a result,the ZnCo anode achieves a Coulombic efficiency of 99.2%over 1300 cycles,and the ZnCo symmetric cell exhibits a long cycle life of over 2000 h at 4.4 mA cm^(-2).Importantly,the ZnCo//NH_(4)V_(4)O_(10)full cell retains a high discharge capacity of 218.4 mAh g^(-1)after 800 cycles.Meanwhile,the ZnFe-based symmetric cell also displays excellent cycling stability over 2500 h at 1.77 mA cm^(-2).This strategy provides a facile anode modification approach toward high-performance AZIBs.展开更多
Aqueous zinc-ion batteries(AZIBs)are pivotal for achieving net-zero goals,yet their commercialization is impeded by zinc dendrites,parasitic reactions,and interfacial instability.Current debates persist on the interpl...Aqueous zinc-ion batteries(AZIBs)are pivotal for achieving net-zero goals,yet their commercialization is impeded by zinc dendrites,parasitic reactions,and interfacial instability.Current debates persist on the interplay between zincophilic-hydrophilic and zincophobic-hydrophobic interactions at the anode-electrolyte interface.Herein,a conceptual framework that decouples these competing effects was proposed,enabling the rational design of a dual-layer architecture with an inner zincophilic layer for Zn^(2+)flux homogenization and an outer hydrophobic layer for water shielding.Through in situ and ex situ analyses,the synergistic mechanism was elucidated.During the cycling process,the zincophilic interface guides uniform Zn deposition,while the hydrophobic coating suppresses H_(2)O-induced side reactions.This dual modification achieves a Zn||Cu cell with an unprecedented 99.89%Coulombic efficiency and 975-cycle stability.This work resolves the long-standing controversy over interfacial affinity design,offering a scalable and industrially viable strategy to enhance AZIBs’durability without sacrificing energy density.展开更多
Aqueous zinc-iodine(Zn-I_(2))batteries show great potential as energy storage candidates due to their high-safety and low-cost,but confronts hydrogen evolution reaction(HER)and dendrite growth at anode side and polyio...Aqueous zinc-iodine(Zn-I_(2))batteries show great potential as energy storage candidates due to their high-safety and low-cost,but confronts hydrogen evolution reaction(HER)and dendrite growth at anode side and polyiodide shuttling at cathode side.Herein,"tennis racket"(TR)hydrogel electrolytes were prepared by the co-polymerization and co-blending of polyacrylamide(PAM),sodium lignosulfonate(SL),and sodium alginate(SA)to synchronously regulate cathode and anode of Zn-I_(2)batteries."Gridline structure"of TR can induce the uniform transportation of Zn^(2+)ions through the coordination effect to hinder HER and dendrite growth at anode side,as well as hit I_(3)^(-)ions as"tennis"via the strong repulsion force to avoid shuttle effect at cathode side.The synergistic effect of TR electrolyte endows Zn-Zn symmetric battery with high cycling stability over 4500 h and Zn-I_(2)cell with the stably cycling life of 15000 cycles at5 A g^(-1),outperforming the reported works.The practicability of TR electrolyte is verified by flexible Zn-I_(2)pouch battery.This work opens a route to synchronously regulate cathode and anode to enhance the electrochemical performance of Zn-I_(2)batteries.展开更多
Aqueous zinc ion batteries(AZIBs)have attracted widespread attention due to their unique advantages.However,the growth of dendrites on the anode and the occurrence of side reactions limits the improvement of electroch...Aqueous zinc ion batteries(AZIBs)have attracted widespread attention due to their unique advantages.However,the growth of dendrites on the anode and the occurrence of side reactions limits the improvement of electrochemical performance of AZIBs.The alloying of zinc anode effectively alleviates above problems,which is beneficial to the long-term cycle performance of AZIBs.In this study,zinc-copper alloy anode(Cu@Zn)was synthesized by melting method.The method is not only simple and easy to operate,but also can make the synthesized anode Cu element uniform distribution and improve the corrosion resistance of the anode.At the same time,the Cu@Zn surface reconstructed has a large proportion of Zn(002)crystal surface exposure,with the zinc affinity of Cu.Both of them can induce the uniform deposition of Zn2+ions along the Zn(002)crystal plane,further inhibiting the growth of dendrite.The Cu@Zn//Cu@Zn symmetrical batteries can cycle more than 1000 times at current densities of 0.3 and 1.2 mA cm^(-2),and maintain a relatively low hysteresis voltage.And the discharge capacity retention rate of Cu@Zn//MnO_(2)maintains 84.64%at 2.0 A g^(-1)after 1000 cycles.This study provides a new methodological reference for the development of advanced AZIBs anodes.展开更多
Dendrite formation and side reactions,which originate from uncontrolled zinc(Zn)nucleation and growth and high water activity,remain the two critical challenges that hinder the practical implementation of Zn anodes fo...Dendrite formation and side reactions,which originate from uncontrolled zinc(Zn)nucleation and growth and high water activity,remain the two critical challenges that hinder the practical implementation of Zn anodes for rechargeable aqueous batteries.In this work,we propose a cation and anion comodulation strategy to realize highly textured and durable Zn anodes.As a proof of concept,1-ethyl-1-methylpyrrolidinium bromide(MEPBr)is selected as a versatile additive to regulate Zn deposition.Specifically,MEP^(+)cations with preferential adsorption on tips/edges first promote uniform primary Zn nucleation on the substrate,followed by dynamic“edge shielding”of existing deposits to guide highly oriented Zn growth.Meanwhile,the incorporation of Br^(-)anions promotes the enrichment of Zn^(2+)at the electrode-electrolyte interface(EEI),thereby facilitating Zn deposition kinetics.In addition,both the preferentially adsorbed MEP^(+)cations and Br^(-)anions create a water-poor EEI while the two ionic species disrupt the original hydrogen bond network and reduce water within the solvation structure in the bulk electrolyte through ion-water interactions,thus dramatically reducing water-induced side reactions.As a result,the Zn//Zn symmetric battery with the MEPBr-modulated electrolyte exhibits a remarkable lifespan of over 4000 h at 2 m A cm^(-2)and 1 mA h cm^(-2).More excitingly,the newly designed electrolyte enables a Zn//NaV_(3)O_(8)·1.5H_(2)O full battery with a thin Zn anode(50μm)and a high mass-loading cathode(~10 mg cm^(-2))to operate normally for over 300 cycles with remarkable capacity retention,showcasing its great potential for practical applications.展开更多
The preferential proton reduction over zinc-ion deposition in aqueous batteries arises from dual yet conflicting roles of water as charge carrier and parasitic reactant,posing persistent interfacial challenges.Althoug...The preferential proton reduction over zinc-ion deposition in aqueous batteries arises from dual yet conflicting roles of water as charge carrier and parasitic reactant,posing persistent interfacial challenges.Although cosolvent engineering has shown promise in mitigating water activity through hydrogenbond network modulation,prevailing strategies remain limited by their narrow focus on electronic and functional group properties,neglecting the stereochemical influence on molecular assembly.In this work,we uncover how molecular chirality dictates the hierarchical organization of hydrogen-bonding networks between cosolvents and water,which is a critical but previously unrecognized determinant of interfacial stability.By interrogating enantiomeric pairs(L-/D-carnitine),we demonstrate that chiral constraints steer the spatial arrangement of hydration structures through stereoselective hydrogenbonding geometries.Combined spectroscopic and molecular dynamics analyses reveal that L-carnitine(L-CN)forms a three-dimensional hydrogen-bonded matrix with water,exhibiting superior directional connectivity relative to its D-isomer.This stereo-dependent architecture simultaneously reinforces Zn2+solvation shells via bridging H-bond interactions and generates a self-adaptive interfacial structure that kinetically isolates water from the zinc anode surface.This stereochemical optimization enables Zn||Zn symmetric cells with unprecedented cycling stability exceeding 2000 h at 0.5 mA cm^(-2)/0.5 mAh cm^(-2).Corresponding Zn||Cu asymmetric cells maintain a high average Coulombic efficiency of 99.7%over 500 cycles at 3.0 mA cm^(-2)/3.0 mAh cm^(-2).This study pioneers a stereochemical design framework for aqueous electrolytes,elucidating chiral recognition mechanisms in solvation structures and establishing molecular topology engineering as a transformative strategy for high-efficiency energy storage systems.展开更多
Zinc is recognized as a vital biological element for animals and plants.Both zinc deficiency and excess will cause damage to cells,and zinc deficiency in the human body may lead to severe health problems.Zinc deficien...Zinc is recognized as a vital biological element for animals and plants.Both zinc deficiency and excess will cause damage to cells,and zinc deficiency in the human body may lead to severe health problems.Zinc deficiency has been identified as a global nutritional issue.Wheat,one of the most significant food crops for humans,is primarily planted in potentially zinc-deficient,calcareous soils in China.It proves to be a major global challenge to increase the zinc concentration in wheat crops to boost crop yields and improve human health.This study investigated the growth process of wheat in calcareous soils with various zinc concentrations using outdoor pot experiments and systematically explored the characteristics and mechanism of zinc transport in the soil-wheat system.The results indicate that the zinc concentrations in various wheat organs decreased in the order of roots,stems,and leaves in the jointing stage and in the order of seeds,roots,and stems in the mature stage.Overall,the zinc enrichment in various wheat organs decreased in the order of seeds,roots,stems,and leaves.In the case of zinc deficiency in soils,wheat roots exhibited elevated zinc availability in the rhizosphere by secreting phytosiderophores.This enhances the zinc uptake capacity of wheat roots.In the case of sufficient zinc supply from soils,chelated zinc formed with citric acid as the chelating ligand occurred stably in soils,contributing to enhanced utilization and uptake rates of zinc,along with elevated transport and enrichment capacities of zinc inside the plants.The results indicate that the zinc concentration in wheat seeds can be somewhat enhanced by regulating the background value of bioavailable zinc concentration in soils.A moderate zinc concentration gradient of 1.0 mg/kg is unfavorable for zinc accumulation in wheat seeds,while a high zinc concentration gradient of 6.0 mg/kg corresponds to the highest degree of zinc enrichment in wheat seeds.This study holds critical scientific significance for enhancing the zinc supply capacity of soils,increasing the zinc concentrations in wheat seeds,and,accordingly,addressing zinc deficiency in the human body.Additionally,this study offers a mechanistic reference and basis for research on the interplay between soils,plants,and human health.展开更多
Aqueous zinc-ion batteries have emerged as promising candidates in next-generation energy storage sys-tems.However,their practical implementation is significantly hindered by interfacial side reactions,par-ticularly t...Aqueous zinc-ion batteries have emerged as promising candidates in next-generation energy storage sys-tems.However,their practical implementation is significantly hindered by interfacial side reactions,par-ticularly the hydrogen evolution reaction(HER)at the Zn metal anode interface.Herein,this study presents an innovative approach to address this challenge through the construction of an interfacial pref-erential coordination layer on the Zn anode surface.The proposed layer effectively terminates the conti-nuity of interfacial hydrogen-bond networks and blocks proton transport,thereby mitigating the HER.Specifically,2-phenylbenzimidazole-5-sulfonic acid(PBSA)with zincophilic groups was introduced as an electrolyte additive,which would be preferentially and selectively anchored on the Zn surface through its zincophilic nitrogen and sulfonic acid,forming the interfacial coordination layer.This coordination layer serves as a protective barrier,repelling water molecules from the Zn electrode surface and alleviat-ing water decomposition.Crucially,the interfacial coordination layer features stronger hydrogen-bonding interactions with interfacial water molecules,terminates the hydrogen-bonding network between water molecules,hinders the transportation and electro-reduction of proton,and ultimately inhibits HER at the interface.As a result,the Zn symmetric cell with PBSA/ZnSO_(4)delivered higher cycling stability of 2500 h at 1 mA cm^(-2)and Zn/NH_(4)V_(4)O_(10)full cells with PBSA/ZnSO_(4)possessed enhanced capac-ity retention.This interfacial hydrogen-bond regulation strategy provided valuable insight for designing HER-free interfacial protective layer in high-performance aqueous batteries.展开更多
基金support from the Australian Research Council Discovery Program(DP220103416,DP240102177)Australian Research Council Future Fellowships(FT200100730,FT210100804).
文摘Aqueous zinc(Zn)-ion batteries hold great promise as renewable energy storage system for carbon-neutral energy transition.However,Zn anodes suffer from poor Zn plating/stripping reversibility due to Zn dendrite growth and side reactions.Existing Zn interfacial modification strategies based on single-component or homogeneous structure are insufficient to address these issues comprehensively.Herein,we rationally designed an organic-inorganic hybrid interfacial layer with rigid-to-soft graded structure for dendrite-free and stable Zn anodes.A liquid plasma-assisted oxidation technology is developed to rapidly construct a porous ZnO inner framework in situ.This ZnO layer offers high interfacial energy,mechanical robustness,and an open structure that facilitates ion transport while firmly anchoring a subsequently coated soft polymer layer.The resulting architecture presents a structurally graded and functionally complementary interface,enabling effective dendrite suppression,continuous Zn ion transport,and enhanced corrosion resistance.As a result,a long cycling stability of more than 6000 h can be achieved at 1 mA cm^(-2)for 1 mAh cm^(-2)in symmetric cells.When used as anodes for zinc-iodine full battery,the hybrid interlayer can effectively prevent the Zn anodes from the corrosion by polyiodine,enabling stable cycling and negligible capacity decay(~0.02‰per cycle)for over 10,000 cycles at 2.0 A g^(-1).This work demonstrates a promising interfacial design strategy and introduces a novel liquid plasma-assisted oxidation route for fabricating high-performance Zn anodes towards next-generation aqueous batteries.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFD1200702)the Sanya Fanxing Technology Special Program,China(Grant No.2024KJFX023)the Shandong Provincial Key Research and Development Program,China(Grant No.2023LZGCQY018).
文摘Zinc(Zn)deficiency is a global health issue,exacerbated by low Zn concentration and poor bioavailability in rice,primarily due to phytic acid(PA)interference.In this study,four doubled haploid(DH)progenies(DH1,DH11,DH18,and DH29)with distinct Zn and PA profiles were used to evaluate the effects of varying degrees of milling(DOM)on Zn bioavailability.Results showed DOM followed a double-exponential decay pattern(R^(2)>0.99)with milling time,varying among the four DH lines under identical milling conditions.As DOM increased,Zn,PA,and phosphorus(P)concentrations decreased progressively.
基金the financial support from Research Institute for Smart Energy at the Hong Kong Polytechnic University(Grant No.CDB2)the support of the Hong Kong PhD Fellowship Scheme(Grant No.PF21-65328)。
文摘Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage,but their commercialization is hindered by zinc anode challenges,notably parasitic reactions and dendrite growth.Herein,we present a biodegradable biomass-derived protective layer,primarily composed of curcumin,as a zincophilic interface for AZMBs.The curcumin-based layer,fabricated via a homogeneous solution process,exhibits strong adhesion,uniform coverage,and robust mechanical integrity.Rich polar functional groups in curcumin facilitate homogeneous Zn~(2+)flux and suppress side reactions.The curcumin-based layer shows a favorable affinity for zinc trifluoromethanesulfonate(Zn(OTf)_(2))electrolyte,which is the representative of organic zinc salts,enabling optimal thickness for both protection and ion transport.The protected Zn anodes demonstrate an extended lifespan of 2500 h in symmetrical cells and a high Coulombic efficiency of 99.15%.Furthermore,Zn(OTf)_(2)-based system typically exhibits poor stability at high current densities.Fortunately,the lifespan of symmetrical cells was extended by 40-fold at the high current density.When paired with an Na V_(3)O_(8)·1.5H_(2)O(NVO)cathode,the system achieves 86.5%capacity retention after 3000 cycles at a large specific current density of 10 A g^(-1).These results underscore the efficacy of the curcumin-based protective layer in enhancing the reversibility and stability of metal electrodes,specifically relieving the instability of Zn(OTf)_(2)-based systems at high current densities,advancing its commercial viability.
基金supported by the Natural Science Foundation of China(Nos.52125202,52202100,and U24A2065)the Natural Science Foundation of Jiangsu Province(BK20243016)Fundamental Research Funds for the Central Universities,China Postdoctoral Science Foundation(No.2024T171166).
文摘Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.
基金supported by the Anhui Provincial Science and Technology Innovation Initiative(202423i08050051)the Anhui Provincial Natural Science Foundation(2408085MB029)+1 种基金the HFIPS Director’s Fund(YZJJGGZX202201)the Natural Science Foundation of Hebei Province of China(B2024402018)。
文摘Aqueous zinc-ion batteries(AZIBs)are currently confronted with the challenge of achieving long-term cyclic stability under high current densities.This issue is primarily attributed to the excessive growth of dendrites and the occurrence of significant side reactions.Herein,sucralose(SCL),as an electrolyte additive,has been used to promote the exposure of the Zn(002)texture.The introduction of SCL can adjust the Zn~(2+)nucleation and diffusion along different crystal facets,promoting the exposure of the Zn(002)texture.By substituting water molecules in the[Zn(H_(2)O)_(6)]~(2+),SCL reconfigures the hydrogen bond network in the electrolyte,reconstructing the solvation structure and suppressing the hydrogen evolution reaction.Consequently,the Zn//Zn symmetric battery exhibits long-term cycling stability of over 4900 h at 1 mA cm^(-2)-1 mAh cm^(-2).Even at a harsh condition of 30 mA cm^(-2)-30 mAh cm^(-2)(DOD=73.3%),it can stably cycle for 171 h.The CE of the Zn//Cu half battery reaches 99.61% at 0.2 mA cm^(-2)with 0.2 mAh cm^(-2).Employing the optimized electrolyte,after 500 cycles,a high specific capacity of 420 mAh g^(-1)can be retained for the NH_4V_4O_(10)//Zn full battery at 500 mA g^(-1),corresponding to a capacity retention of 90.7%.
基金supported by the National Key R&D Program of China(No.2023YFA1507500)the Nation-al Natural Science Foundation of China(No.52373159)。
文摘Green solvent pretreatment of biomass represents a promising ap-proach for enhancing the econom-ic value of lignocellulosic deriva-tives.In this study,corncob biomass was treated with a diol-based deep eutectic solvent(DES)under mild conditions,facilitating efficient cellulose separation.The extracted cellulose was subsequently used to fabricate cellulose hydrogels in an aqueous zinc chloride solution.The resulting hydrogel exhibited a“water-in-salt”effect due to the high concentration of ZnCl_(2).Leveraging the antifreeze properties of sorbitol,the system demon-strated outstanding low-temperature electrochemical performance,including a broad operat-ing voltage window and an ionic conductivity of 38.4 mS·cm^(-1)at-20℃.At 20℃,the de-vice achieved an energy density of 206 Wh·kg^(-1)and a power density of 2701.05 W·kg^(-1)at a current density of 1 A·g^(-1).Moreover,the flexible zinc-ion hybrid supercapacitor(ZHSC)maintained 89%of its capacitance and nearly 100%Coulombic efficiency after 5500 cycles at 20℃.This work not only advances the development of zinc-ion energy storage devices but al-so establishes a new paradigm for the green and direct utilization of biomass-derived materi-als.
基金supported by the Major Basic Research Projects of Shandong Natural Science Foundation(ZR2024ZD37)the Taishan Scholar Program of Shandong Province,China(No.tsqn202211048)+3 种基金the National Natural Science Foundation of China(No.22179123,22579155)the National Science Fund for Distinguished Young Scholars(52125305)the Science and Technology Key Project of Wuhan(No.2023010302020030)and the Science and Technology Major Project of Xinjiang Autonomous Region(No.2022A03009).
文摘Zinc-ion hybrid supercapacitors(ZIHCs)are compelling candidates for next-generation energy storage owing to their intrinsic safety,low cost,and high power density.However,their practical implementation remains hindered by the limited energy density of traditional carbon-based cathodes.Here,we rationally design porous carbon nanofibers embedded with atomically dispersed Zn and Fe dual-metal sites(ZnFe/PCNFs),synthesized via electrospinning followed by controlled carbonization.The introduction of Fe modulates the local electronic structure of Zn centers,thereby facilitating enhanced d-orbital hybridization and stronger ion adsorption through the formation of ZnFeN_(6) coordination motifs.Coupled with high surface area and hierarchical porosity,these atomic-level interactions facilitate exceptional ion accessibility and rapid charge-transfer kinetics.As a cathode for ZIHCs,ZnFe/PCNFs deliver a specific capacity of 213 mAh g^(-1),exceptional high-rate capability,and longterm cycling stability over 20000 cycles.This work elucidates mechanisms of dual-metal atomic coordination and provides a robust design strategy for high-performance,durable aqueous energy storage systems.
基金supported by the National Natural Science Foundation of China(52471240)the Natural Science Foundation of Zhejiang Province(LZ23B030003)+2 种基金the Fundamental Research Funds for the Central Universities(226-2024-00075)support from the Engineering and Physical Sciences Research Council(EPSRC,UK)RiR grant-RIR18221018-1EU COST CA23155。
文摘The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.
基金financially supported by the Science and Technology Development Project of Henan Province,China(No.242102241042)the Joint Fund of Henan Province Science and Technology R&D Program(No.225200810093)+1 种基金the Startup Research of Henan Academy of Sciences(No.231817001)the Key Innovation Projects for Postgraduates of Henan Academy of Sciences(No.24331712)。
文摘Aqueous zinc-ion batteries are regarded as promising electrochemical energy-storage systems for various applications because of their high safety,low costs,and high capacities.However,dendrite formation and side reactions during zinc plating or stripping greatly reduce the capacity and cycle life of a battery and subsequently limit its practical application.To address these issues,we modified the surface of a zinc anode with a functional bilayer composed of zincophilic Cu and flexible polymer layers.The zincophilic Cu interfacial layer was prepared through CuSO_(4)solution pretreatment to serve as a nucleation site to facilitate uniform Zn deposition.Meanwhile,the polymer layer was coated onto the Cu interface layer to serve as a protective layer that would prevent side reactions between zinc and electrolytes.Benefiting from the synergistic effect of the zincophilic Cu and protective polymer layers,the symmetric battery exhibits an impressive cycle life,lasting over 2900 h at a current density of 1 m A·cm^(-2)with a capacity of 1 m A·h·cm^(-2).Moreover,a full battery paired with a vanadium oxide cathode achieves a remarkable capacity retention of 72%even after 500 cycles.
基金partially supported by the National Natural Science Foundation of China(22479022)Liaoning Revitalization Talents Program(XLYC2007129)。
文摘Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aqueous electrolytes.A zincophilic carbon(ZC)layer was deposited on a Zn metal foil at 450°C by the up-stream pyrolysis of a hydrogen-bonded supramolecular substance framework,as-sembled from melamine(ME)and cyanuric acid(CA).The zincophilic groups(C=O and C=N)in the ZC layer guide uniform zinc plating/stripping and eliminate dendrites and side reactions.so that assembled symmetrical batteries(ZC@Zn//ZC@Zn)have a long-term service life of 2500 h at 1 mA cm^(−2) and 1 mAh cm^(−2),which is much longer than that of bare Zn anodes(180 h).In addition,ZC@Zn//V2O5 full batteries have a higher capacity of 174 mAh g^(−1) after 1200 cycles at 2 A g^(−1) than a Zn//V_(2)O_(5) counterpart(100 mAh g^(−1)).The strategy developed for the low-temperat-ure deposition of the ZC layer is a new way to construct advanced zinc metal anodes for ZMBs.
基金supported by the National Key R&D Program of China(Grant No.2022YFE0139400)the National Natural Science Foundation of China(Grant No.31961143016)the Shenzhen Science and Technology Program,China(Grant No.JCYJ20200109150650397).
文摘Zinc(Zn)is an essential micronutrient for both plants and humans.Zn deficiency is common in many paddy fields and reduces yield and grain Zn content(GZC).To accelerate breeding for improved GZC and Zn deficiency tolerance(ZDT)rice varieties,it is important to identify genes regulating Zn homeostasis.In this study,a member of the Ser/Thr protein phosphatase family,LOC_Os07g48840(named as OsGZ7),was found to contributed to ZDT and GZC in rice.The expression of OsGZ7 in roots and shoots was inhibited by Zn deficiency and toxicity,but induced by iron(Fe),manganese(Mn),and copper(Cu)deficiency,as well as chromium toxicity.OsGZ7 localized to the cytoplasm and was expressed in all tissues during the tillering,flowering,and grain-filling stages,particularly in the leaf blade and leaf sheath.At the seedling stage,knockout of OsGZ7 enhanced ZDT and increased Zn accumulation in both roots and shoots.At the maturity stage,knockout of OsGZ7 enhanced GZC,while overexpression of OsGZ7 reduced GZC.RNA-seq analysis suggested that OsGZ7 might regulate Zn homeostasis by affecting metal binding,hormone signal transduction,and oxidoreductase activity.Taken together,our findings indicate that OsGZ7 contributes to ZDT and Zn accumulation in rice.
基金supported by the Scientific Research and Technology Development Project of China National Petroleum Corporation(Grant Nos.2024ZG50,2022DQ03-03)the National Natural Science Foundation of China(Grant Nos.52372252)the Science and Technology Innovation Program of Hunan Province(Grant Nos.2024RC1022).
文摘Dendrite growth represents one of the most significant challenges that impede the development of aqueous zinc-ion batteries.Herein,Gd^(3+)ions are introduced into conventional electrolytes as a microlevelling agent to achieve dendrite-free zinc electrodeposition.Simulation and experimental results demonstrate that these Gd^(3+)ions are preferentially adsorbed onto the zinc surface,which enables dendritefree zinc anodes by activating the microlevelling effect during electrodeposition.In addition,the Gd^(3+)additives effectively inhibit side reactions and facilitate the desolvation of[Zn(H_(2)O)_(6)]^(2+),leading to highly reversible zinc plating/stripping.Due to these improvements,the zinc anode demonstrates a significantly prolonged cycle life of 2100 h and achieves an exceptional average Coulombic efficiency of 99.72%over 1400 cycles.More importantly,the Zn//NH_(4)V_(4)O_(10)full cell shows a high capacity retention rate of 85.6%after 1000 cycles.This work not only broadens the application of metallic cations in battery electrolytes but also provides fundamental insights into their working mechanisms.
基金supported by the Prospective Basic Research Projects of CNPC(Grant Nos.2022DJ5406,2022DJ5407,2022DJ5408,2022DJ4507,TGRI-2021-1,2022DQ03-03).
文摘Aqueous zinc-ion batteries(AZIBs)present a promising option for next-generation batteries given their high safety,eco-friendliness,and resource sustainability.Nonetheless,the practical application of zinc anodes is hindered by inevitable parasitic reactions and dendrite growth.Here,zinc alloy layers(i.e.,ZnCo and ZnFe alloys)were rationally constructed on the zinc surface by chemical displacement reactions.The alloying process exposes more(002)planes of the ZnCo anode to guide the preferential and dendrite-free zinc deposition.Furthermore,the ZnCo alloy layer not only effectively inhibits water-induced side reactions but also accelerates electrode kinetics,enabling highly reversible zinc plating/stripping.As a result,the ZnCo anode achieves a Coulombic efficiency of 99.2%over 1300 cycles,and the ZnCo symmetric cell exhibits a long cycle life of over 2000 h at 4.4 mA cm^(-2).Importantly,the ZnCo//NH_(4)V_(4)O_(10)full cell retains a high discharge capacity of 218.4 mAh g^(-1)after 800 cycles.Meanwhile,the ZnFe-based symmetric cell also displays excellent cycling stability over 2500 h at 1.77 mA cm^(-2).This strategy provides a facile anode modification approach toward high-performance AZIBs.
基金supported by the National Natural Science Foundation of China(U2130204)the Joint Funds of the National Key R&D Program of China(2022YFB2502102)+1 种基金the Young Elite Scientists Sponsorship Program by CAST(YESS20200364)the Beijing Outstanding Young Scientists Program(BJJWZYJH01201910007023)。
文摘Aqueous zinc-ion batteries(AZIBs)are pivotal for achieving net-zero goals,yet their commercialization is impeded by zinc dendrites,parasitic reactions,and interfacial instability.Current debates persist on the interplay between zincophilic-hydrophilic and zincophobic-hydrophobic interactions at the anode-electrolyte interface.Herein,a conceptual framework that decouples these competing effects was proposed,enabling the rational design of a dual-layer architecture with an inner zincophilic layer for Zn^(2+)flux homogenization and an outer hydrophobic layer for water shielding.Through in situ and ex situ analyses,the synergistic mechanism was elucidated.During the cycling process,the zincophilic interface guides uniform Zn deposition,while the hydrophobic coating suppresses H_(2)O-induced side reactions.This dual modification achieves a Zn||Cu cell with an unprecedented 99.89%Coulombic efficiency and 975-cycle stability.This work resolves the long-standing controversy over interfacial affinity design,offering a scalable and industrially viable strategy to enhance AZIBs’durability without sacrificing energy density.
基金financially supported by the Energy Revolution S&T Program of Yulin Innovation Institute of Clean Energy(E411060316)the NSFC-CONICFT Joint Project(51961125207)+1 种基金the Special Fund(2024)of Basic Scientific Research Project at Undergraduate University in Liaoning Province(LJ212410152056)the Foundation(GZKF202301)of State Key Laboratory of Biobased Material and Green Papermaking,Qilu University of Technology,Shandong Academy of Sciences。
文摘Aqueous zinc-iodine(Zn-I_(2))batteries show great potential as energy storage candidates due to their high-safety and low-cost,but confronts hydrogen evolution reaction(HER)and dendrite growth at anode side and polyiodide shuttling at cathode side.Herein,"tennis racket"(TR)hydrogel electrolytes were prepared by the co-polymerization and co-blending of polyacrylamide(PAM),sodium lignosulfonate(SL),and sodium alginate(SA)to synchronously regulate cathode and anode of Zn-I_(2)batteries."Gridline structure"of TR can induce the uniform transportation of Zn^(2+)ions through the coordination effect to hinder HER and dendrite growth at anode side,as well as hit I_(3)^(-)ions as"tennis"via the strong repulsion force to avoid shuttle effect at cathode side.The synergistic effect of TR electrolyte endows Zn-Zn symmetric battery with high cycling stability over 4500 h and Zn-I_(2)cell with the stably cycling life of 15000 cycles at5 A g^(-1),outperforming the reported works.The practicability of TR electrolyte is verified by flexible Zn-I_(2)pouch battery.This work opens a route to synchronously regulate cathode and anode to enhance the electrochemical performance of Zn-I_(2)batteries.
基金financially supported by Natural Science Foundation of Hebei Province(Nos.E2024209118,B2022209026)Central Guided Local Science and Technology Development Funding Program(No.246Z4414G)+2 种基金Key Research Project Focused on Basic Research of Hebei Province Education Department(No.JZX2024026)Science and Technology Planning Project of Tangshan City(No.24130217C)Youth Scholars Promotion Plan of North China University of Science and Technology(No.QNTJ202309)
文摘Aqueous zinc ion batteries(AZIBs)have attracted widespread attention due to their unique advantages.However,the growth of dendrites on the anode and the occurrence of side reactions limits the improvement of electrochemical performance of AZIBs.The alloying of zinc anode effectively alleviates above problems,which is beneficial to the long-term cycle performance of AZIBs.In this study,zinc-copper alloy anode(Cu@Zn)was synthesized by melting method.The method is not only simple and easy to operate,but also can make the synthesized anode Cu element uniform distribution and improve the corrosion resistance of the anode.At the same time,the Cu@Zn surface reconstructed has a large proportion of Zn(002)crystal surface exposure,with the zinc affinity of Cu.Both of them can induce the uniform deposition of Zn2+ions along the Zn(002)crystal plane,further inhibiting the growth of dendrite.The Cu@Zn//Cu@Zn symmetrical batteries can cycle more than 1000 times at current densities of 0.3 and 1.2 mA cm^(-2),and maintain a relatively low hysteresis voltage.And the discharge capacity retention rate of Cu@Zn//MnO_(2)maintains 84.64%at 2.0 A g^(-1)after 1000 cycles.This study provides a new methodological reference for the development of advanced AZIBs anodes.
基金supported by the Research Grants Council of the Hong Kong Special Administrative Region,China(16205721)the PolyU Start-up Fund(1-BDC4)。
文摘Dendrite formation and side reactions,which originate from uncontrolled zinc(Zn)nucleation and growth and high water activity,remain the two critical challenges that hinder the practical implementation of Zn anodes for rechargeable aqueous batteries.In this work,we propose a cation and anion comodulation strategy to realize highly textured and durable Zn anodes.As a proof of concept,1-ethyl-1-methylpyrrolidinium bromide(MEPBr)is selected as a versatile additive to regulate Zn deposition.Specifically,MEP^(+)cations with preferential adsorption on tips/edges first promote uniform primary Zn nucleation on the substrate,followed by dynamic“edge shielding”of existing deposits to guide highly oriented Zn growth.Meanwhile,the incorporation of Br^(-)anions promotes the enrichment of Zn^(2+)at the electrode-electrolyte interface(EEI),thereby facilitating Zn deposition kinetics.In addition,both the preferentially adsorbed MEP^(+)cations and Br^(-)anions create a water-poor EEI while the two ionic species disrupt the original hydrogen bond network and reduce water within the solvation structure in the bulk electrolyte through ion-water interactions,thus dramatically reducing water-induced side reactions.As a result,the Zn//Zn symmetric battery with the MEPBr-modulated electrolyte exhibits a remarkable lifespan of over 4000 h at 2 m A cm^(-2)and 1 mA h cm^(-2).More excitingly,the newly designed electrolyte enables a Zn//NaV_(3)O_(8)·1.5H_(2)O full battery with a thin Zn anode(50μm)and a high mass-loading cathode(~10 mg cm^(-2))to operate normally for over 300 cycles with remarkable capacity retention,showcasing its great potential for practical applications.
基金supported by the National Natural Science Foundation of China(52402316)the Natural Science Foundation of Zhejiang Province(LQ23B030002)the Start-up Foundation of Zhejiang University of Science and Technology(ZUST)。
文摘The preferential proton reduction over zinc-ion deposition in aqueous batteries arises from dual yet conflicting roles of water as charge carrier and parasitic reactant,posing persistent interfacial challenges.Although cosolvent engineering has shown promise in mitigating water activity through hydrogenbond network modulation,prevailing strategies remain limited by their narrow focus on electronic and functional group properties,neglecting the stereochemical influence on molecular assembly.In this work,we uncover how molecular chirality dictates the hierarchical organization of hydrogen-bonding networks between cosolvents and water,which is a critical but previously unrecognized determinant of interfacial stability.By interrogating enantiomeric pairs(L-/D-carnitine),we demonstrate that chiral constraints steer the spatial arrangement of hydration structures through stereoselective hydrogenbonding geometries.Combined spectroscopic and molecular dynamics analyses reveal that L-carnitine(L-CN)forms a three-dimensional hydrogen-bonded matrix with water,exhibiting superior directional connectivity relative to its D-isomer.This stereo-dependent architecture simultaneously reinforces Zn2+solvation shells via bridging H-bond interactions and generates a self-adaptive interfacial structure that kinetically isolates water from the zinc anode surface.This stereochemical optimization enables Zn||Zn symmetric cells with unprecedented cycling stability exceeding 2000 h at 0.5 mA cm^(-2)/0.5 mAh cm^(-2).Corresponding Zn||Cu asymmetric cells maintain a high average Coulombic efficiency of 99.7%over 500 cycles at 3.0 mA cm^(-2)/3.0 mAh cm^(-2).This study pioneers a stereochemical design framework for aqueous electrolytes,elucidating chiral recognition mechanisms in solvation structures and establishing molecular topology engineering as a transformative strategy for high-efficiency energy storage systems.
基金supported by a general project of the National Natural Science Foundation of China(42272346)a project initiated by the China Geological Survey(DD20230101).
文摘Zinc is recognized as a vital biological element for animals and plants.Both zinc deficiency and excess will cause damage to cells,and zinc deficiency in the human body may lead to severe health problems.Zinc deficiency has been identified as a global nutritional issue.Wheat,one of the most significant food crops for humans,is primarily planted in potentially zinc-deficient,calcareous soils in China.It proves to be a major global challenge to increase the zinc concentration in wheat crops to boost crop yields and improve human health.This study investigated the growth process of wheat in calcareous soils with various zinc concentrations using outdoor pot experiments and systematically explored the characteristics and mechanism of zinc transport in the soil-wheat system.The results indicate that the zinc concentrations in various wheat organs decreased in the order of roots,stems,and leaves in the jointing stage and in the order of seeds,roots,and stems in the mature stage.Overall,the zinc enrichment in various wheat organs decreased in the order of seeds,roots,stems,and leaves.In the case of zinc deficiency in soils,wheat roots exhibited elevated zinc availability in the rhizosphere by secreting phytosiderophores.This enhances the zinc uptake capacity of wheat roots.In the case of sufficient zinc supply from soils,chelated zinc formed with citric acid as the chelating ligand occurred stably in soils,contributing to enhanced utilization and uptake rates of zinc,along with elevated transport and enrichment capacities of zinc inside the plants.The results indicate that the zinc concentration in wheat seeds can be somewhat enhanced by regulating the background value of bioavailable zinc concentration in soils.A moderate zinc concentration gradient of 1.0 mg/kg is unfavorable for zinc accumulation in wheat seeds,while a high zinc concentration gradient of 6.0 mg/kg corresponds to the highest degree of zinc enrichment in wheat seeds.This study holds critical scientific significance for enhancing the zinc supply capacity of soils,increasing the zinc concentrations in wheat seeds,and,accordingly,addressing zinc deficiency in the human body.Additionally,this study offers a mechanistic reference and basis for research on the interplay between soils,plants,and human health.
基金supported by financial support from the National Natural Science Foundation of China(Grant No.22225801 and 22461142137).
文摘Aqueous zinc-ion batteries have emerged as promising candidates in next-generation energy storage sys-tems.However,their practical implementation is significantly hindered by interfacial side reactions,par-ticularly the hydrogen evolution reaction(HER)at the Zn metal anode interface.Herein,this study presents an innovative approach to address this challenge through the construction of an interfacial pref-erential coordination layer on the Zn anode surface.The proposed layer effectively terminates the conti-nuity of interfacial hydrogen-bond networks and blocks proton transport,thereby mitigating the HER.Specifically,2-phenylbenzimidazole-5-sulfonic acid(PBSA)with zincophilic groups was introduced as an electrolyte additive,which would be preferentially and selectively anchored on the Zn surface through its zincophilic nitrogen and sulfonic acid,forming the interfacial coordination layer.This coordination layer serves as a protective barrier,repelling water molecules from the Zn electrode surface and alleviat-ing water decomposition.Crucially,the interfacial coordination layer features stronger hydrogen-bonding interactions with interfacial water molecules,terminates the hydrogen-bonding network between water molecules,hinders the transportation and electro-reduction of proton,and ultimately inhibits HER at the interface.As a result,the Zn symmetric cell with PBSA/ZnSO_(4)delivered higher cycling stability of 2500 h at 1 mA cm^(-2)and Zn/NH_(4)V_(4)O_(10)full cells with PBSA/ZnSO_(4)possessed enhanced capac-ity retention.This interfacial hydrogen-bond regulation strategy provided valuable insight for designing HER-free interfacial protective layer in high-performance aqueous batteries.
