Effect of impurities in recycling water on Pb-Ag anode passivation in zinc electrowinning process was investigated by linear scan voltammetry.Results show that passivation process would be affected in the presence of ...Effect of impurities in recycling water on Pb-Ag anode passivation in zinc electrowinning process was investigated by linear scan voltammetry.Results show that passivation process would be affected in the presence of Cl^-and F-in recycling water.It was highly advantageous to take H2SO4 concentration as 180g/L,Mn^2＋ concentration as 3-5 g/L and F-less than 42mg/L.However,passivation process would not be affected when Cl^-concentration was less than 13mg/L without any other ions,or when mass ratio of Mn^2＋ to Cl^-existing in electrolyte was 8,where Cl^-concentration could reach up to 625mg/L.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
The effect of MnO4- and silver content on electrochemical behaviour of five commercial Pb-Ag alloy anodes was studied in acid zinc sulphate electrolyte with and without MnO4- ions at 38 °C during potential decay ...The effect of MnO4- and silver content on electrochemical behaviour of five commercial Pb-Ag alloy anodes was studied in acid zinc sulphate electrolyte with and without MnO4- ions at 38 °C during potential decay periods. When the anodes were immersed into acid zinc sulphate electrolyte without MnO4- ions, the Pb-0.72%Ag anode entered complete passivation state in the shortest time among the five anodes, followed by anodes Pb-0.67%Ag, Pb-0.60%Ag, Pb-0.58%Ag and Pb-0.29%Ag-0.1%Ca by measurement of open circuit potential. During immersion of the anodes, MnO4 ions accelerated the passivation and increased the corrosion current density of the anodes. After immersion in zinc electrolyte with MnO4-, the anode Pb-0.72%Ag had the best corrosion resistance, followed by anodes Pb-0.67%Ag, Pb-0.60%Ag, then the close anodes Pb-0.58%Ag and Pb-0.29%Ag-0.1%Ca by the electrochemical impedance spectroscopy （EIS） analysis.展开更多
Aqueous sodium-ion batteries(ASIBs)have attracted great attention in aqueous batteries due to their merit of high safety.However,the constrained work potential and insufficient chemical stability of anode materials in...Aqueous sodium-ion batteries(ASIBs)have attracted great attention in aqueous batteries due to their merit of high safety.However,the constrained work potential and insufficient chemical stability of anode materials in aqueous electro-lytes hinder the large-scale application of ASIBs.Sodium titanium phosphate,NaTi_(2)(PO_(4))_(3)(NTP),is considered one of the most promising anode materials for ASIBs due to its excellent electrochemical performance and tunable structure.Recently,great achievements have been made in the development of NTP,however,a comprehensive review of existing studies is still lacking.This article firstly introduces the basic properties of NTP and analyzes the existing challenges.Subsequently,it will provide a comprehensive overview of the key strategies related to the design and modification of NTP materials with optimized electrochemical performance.Finally,based on the current research status and practical needs,suggestions,and future perspectives for advancing NTP in practical applications of ASIBs are presented.This review aims to guide the future research trajectory from basic material innovation to industrial applications,thus promoting the large-scale commercializa-tion of ASIBs.展开更多
Niobium-based oxides show great potential in anode materials for fast-charging lithium-ion batteries,but their practical application remains hindered by intrinsically low conductivity.In this study,we successfully syn...Niobium-based oxides show great potential in anode materials for fast-charging lithium-ion batteries,but their practical application remains hindered by intrinsically low conductivity.In this study,we successfully synthesize nano-sized Wadsley-Roth FeNb_(11)O_(29)through Fe-driven phase transformation of Nb_(2)O_(5),which delivers a high specific capacity(280.5 mA h g^(−1)at 0.25 C)along with abundant redox-active sites.Moreover,the Wadsley-Roth shear structure of FeNb_(11)O_(29)facilitates rapid Li^(+)diffusion and guarantees exceptional structural stability.Theoretical calculations further confirm that FeNb_(11)O_(29)has a narrow band gap,which significantly enhances the conductivity.Owing to these merits,FeNb_(11)O_(29)achieves a full charge/discharge cycle within merely 25 s at 75 C rate and retains remarkable cycling stability over 2500 cycles.As a consequence,our assembled FeNb_(11)O_(29)||LiFePO_(4)full cell demonstrates ultra-long cyclability(>10000 cycles)and outstanding fast-charging capability(complete cycling within 2 min at 30 C).These findings highlight nano-sized FeNb_(11)O_(29)as a highly promising anode candidate for next-generation fast-charging LIBs.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
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
Sodium-based dual-ion batteries(SDIBs)have been attracting increasing attention in recent years owing to their low cost,environmental benignancy,and high operating voltage.However,the sluggish ion kinetics of conventi...Sodium-based dual-ion batteries(SDIBs)have been attracting increasing attention in recent years owing to their low cost,environmental benignancy,and high operating voltage.However,the sluggish ion kinetics of conventional carbon anodes that cannot match the fast capacitive anion intercalation behavior of graphite cathodes constraints on improving power density of SDIBs.Herein,we present an ingenious carbon microdomain engineering strategy to fabricate high-performance carbon anode with ion-mediated high-activity nitrogen species and molecular-scale closed-pore architectures.Experimental characterizations and theoretical investigations demonstrate that Zn^(2+)-mediated structural engineering tailors oxidized nitrogen species,which proficiently accelerate the sodium-ion desolvation kinetics;meanwhile the acetate-mediated pore-forming process modulates closed pores,which synergistically afford abundant sodium storage sites for high plateau-region capacity.As a result,the optimized microdomain engineered carbon material(MEC_(3))tailored with the optimal amount of zinc acetate demonstrates an outstanding plateau-region capacity of 253 mAh g^(-1)even at 1 C,among the highest reported values.Consequently,the MEC_(3)||expanded graphite dual-ion battery exhibits an unprecedented cycling stability at high current rate,maintaining 80.6%capacity retention after 10,000 cycles at 10 C,among the best reports.This microdomain engineering strategy provides a new design principle for overcoming kinetic limitations of carbonaceous materials in plateau-dominated sodium storage systems.展开更多
Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on ...Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on energy storage and conversion applications,such as use as anodes in lithium-ion batteries.In this paper,all-inorganic lead-free halide perovskite Cs_(3)Bi_(2)Cl_(9)powders were synthesized by the grinding method,and the lattice was successfully adjusted via introducing Mn^(2+).The characterization results show that Mn-ion substitution can cause local lattice distortion to restructure the lattice,which will cause a mixed arrangement of[BiCl_(6)]octahedra to improve the performance of the anode material.This new material can provide a feasible solution for solving the problem of low specific capacity anode materials caused by unstable crystal structures,and also indicates that such perovskites with unique crystal structures and lattice tunability have broad application prospects in lithium-ion batteries.展开更多
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
The rapid expansion of the photovoltaic industry has generated heavily oxidized waste silicon(wSi),which hinders efficient recycling owing to its small particle size and uncontrolled surface oxidation.This study intro...The rapid expansion of the photovoltaic industry has generated heavily oxidized waste silicon(wSi),which hinders efficient recycling owing to its small particle size and uncontrolled surface oxidation.This study introduces a molten salt electrochemical strategy for converting photovoltaic wSi into NiSi_(2)-silicon nanorods(NiSi_(2)-SiNRs)as high-performance anode materials for lithium-ion batteries.A stable oxidized passivation layer is formed on the wSi surface via controlled oxidation,and further in situ generated highly active NiSi_(2) droplets.The molten salt electric field modulates the surface energy of silicon,while particle integration drives localized directional growth,enabling the self-assembly of NiSi_(2)-SiNRs composites.These NiSi_(2)-SiNRs anodes exhibit rapid ion transport and effective strain buffering.The high aspect ratio of SiNRs and the presence of retained NiSi_(2) facilitate both longitudinal and transverse Li^(+) diffusion.Owing to their robust structural design,the NiSi_(2)-SiNRs anode achieves an excellent initial Coulombic efficiency of 91.61%and retains 72.99%of its capacity after 800 cycles at 2 A·g^(−1).This study establishes a model system for investigating silicide/silicon interfaces in molten salt electrochemical synthesis and provides an effective strategy for upcycling photovoltaic wSi into high-performance lithium-ion battery anodes.展开更多
Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical proper...Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.展开更多
Carbon materials are widely recognized as highly promising electrode materials for various energy storage system applications.Coal tar residues(CTR),as a type of carbon-rich solid waste with high value-added utilizati...Carbon materials are widely recognized as highly promising electrode materials for various energy storage system applications.Coal tar residues(CTR),as a type of carbon-rich solid waste with high value-added utilization,are crucially important for the development of a more sustainable world.In this study,we employed a straightforward direct carbonization method within the temperature range of 700-1000℃to convert the worthless solid waste CTR into economically valuable carbon materials as anodes for potassium-ion batteries(PIBs).The effect of carbonization temperature on the microstructure and the potassium ions storage properties of CTR-derived carbons(CTRCs)were systematically explored by structural and morphological characterization,alongside electrochemical performances assessment.Based on the co-regulation between the turbine layers,crystal structure,pore structure,functional groups,and electrical conductivity of CTR-derived carbon carbonized at 900℃(CTRC-900H),the electrode material with high reversible capacity of 265.6m Ah·g^(-1)at 50 m A·g^(-1),a desirable cycling stability with 93.8%capacity retention even after 100 cycles,and the remarkable rate performance for PIBs were obtained.Furthermore,cyclic voltammetry(CV)at different scan rates and galvanostatic intermittent titration technique(GITT)have been employed to explore the potassium ions storage mechanism and electrochemical kinetics of CTRCs.Results indicate that the electrode behavior is predominantly governed by surface-induced capacitive processes,particularly under high current densities,with the potassium storage mechanism characterized by an“adsorption-weak intercalation”mechanism.This work highlights the potential of CTR-based carbon as a promising electrode material category suitable for high-performance PIBs electrodes,while also provides valuable insights into the new avenues for the high value-added utilization of CTR.展开更多
In this work,the combined addition of strontium/indium(Sr/In)to the magnesium anode for Mg-Air Cells is investigated to improve discharge performance by modifying the anode/electrolyte interface.Indium exists as solid...In this work,the combined addition of strontium/indium(Sr/In)to the magnesium anode for Mg-Air Cells is investigated to improve discharge performance by modifying the anode/electrolyte interface.Indium exists as solid solution atoms in theα-Mg matrix without its second-phase generation,and at the same time facilitates grain refinement,dendritic segregation and Mg17Sr2-phases precipitation.During discharge operation,Sr modifies the film composition via its compounds and promoted the redeposition of In at the substrate/film interface;their co-deposition behavior on the anodic reaction surface enhances anode reaction kinetics,suppresses the negative difference effect(NDE)and mitigates the“chunk effect”(CE),which is contributed to uniform dissolution and low self-corrosion hydrogen evolution rate(HER).Therefore,Mg-Sr-xIn alloy anodes show excellent discharge performance,e.g.,0.5Sr-1.0In shows an average discharge voltage of 1.4234 V and a specific energy density of 1990.71 Wh kg^(-1)at 10 mA cm^(-2).Furthermore,the decisive factor(CE and self-discharge HE)for anodic efficiency are quantitively analyzed,the self-discharge is the main factor of cell efficiency loss.Surprisingly,all Mg-Sr-xIn anodes show anodic efficiency greater than 60%at high current density(≥10 mA cm^(-2)),making them excellent candidate anodes for Mg-Air cells at high-power output.展开更多
Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials ...Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials for SIBs are mainly used as cathodes because of their relatively high redox potentials(>1 V).Organic electrodes with low redox potential that can be used as anode are rare.Herein,a novel organic anode material (tetrasodium 1,4,5,8-naphthalenetetracarboxylate,Na_(4)TDC) has been developed with low redox potential (<0.7 V) and excellent cyclic stability.Its three-sodium storage mechanism was demonstrated with various in-situ/ex-situ spectroscopy and theoretical calculations,showing a high capacity of 208 mAh/g and an average decay rate of merely 0.022%per cycle.Moreover,the Na_(4)TDC-hard carbon composite can further acquire improved capacity and cycling stability for 1200 cycles even with a high mass loading of up to 20 mg cm^(-2).By pairing with a thick Na_(3)V_(2)(PO_(4))_(3)cathode (20.6 mg cm^(-2)),the as-fabricated full cell exhibited high operating voltage (2.8 V),excellent rate performance and cycling stability with a high capacity retention of 88.7% after 200 cycles,well highlighting the Na_(4)TDC anode material for SIBs.展开更多
The dominated contradiction in optimizing the performance of magnesium-air battery anode lies in the difficulty of achieving a good balance between activation and passivation during discharge process.To further reconci...The dominated contradiction in optimizing the performance of magnesium-air battery anode lies in the difficulty of achieving a good balance between activation and passivation during discharge process.To further reconcile this contradiction,two Mg-0.1Sc-0.1Y-0.1Ag anodes with different residual strain distribution through extrusion with/without annealing are fabricated.The results indicate that annealing can significantly lessen the“pseudo-anode”regions,thereby changing the dissolution mode of the matrix and achieving an effective dissolution during discharge.Additionally,p-type semiconductor characteristic of discharge productfilm could suppress the self-corrosion reaction without reducing the polarization of anode.The magnesium-air battery utilizing annealed Mg-0.1Sc-0.1Y-0.1Ag as anode achieves a synergistic improvement in specific capacity(1388.89 mA h g^(-1))and energy density(1960.42 mW h g^(-1)).This anode modification method accelerates the advancement of high efficiency and long lifespan magnesium-air batteries,offering renewable and cost-effective energy solutions for electronics and emergency equipment.展开更多
A novel precipitate-free Mg-0.1Sn anode with a homogeneous equal-axis grain structure was developed and rolled successfully at 573 K.Electrochemical test results indicate that the Mg-0.1Sn alloy exhibits enhanced anod...A novel precipitate-free Mg-0.1Sn anode with a homogeneous equal-axis grain structure was developed and rolled successfully at 573 K.Electrochemical test results indicate that the Mg-0.1Sn alloy exhibits enhanced anode dissolution kinetics.A Mg-air battery prepared using this anode exhibits a cell voltage of 1.626 V at 0.5 mA/cm^(2),reasonable anodic efficiency of 58.17%,and good specific energy of 1730.96 mW·h/g at 10 mA/cm^(2).This performance is attributed to the effective reactive anode surface,the suppressed chunk effect,and weak self-corrosion owing to the homogeneous basal texture.展开更多
An attempt was made to build up a thick and compact oxide layer rapidly by pre-treating the Pb-Ag-Nd anode in fluoride-containing H2SO4 solution. The passivation reaction of Pb-Ag-Nd anode during pre-treatment process...An attempt was made to build up a thick and compact oxide layer rapidly by pre-treating the Pb-Ag-Nd anode in fluoride-containing H2SO4 solution. The passivation reaction of Pb-Ag-Nd anode during pre-treatment process was investigated using cyclic voltammetry, linear scanning voltammetry, environmental scanning electron microscopy and X-ray diffraction analysis. The results show that Pb F2 and PbSO4 are formed near the potential of Pb/PbSO4 couple. The pre-treatment in fluoride-containing H2SO4 solution contributes to the formation of a thick, compact and adherent passive film. Furthermore, pre-treatment in fluoride-containing H2SO4 solution also facilitates the formation of PbO2 on the anodic layer, and the reason could be attributed to the formation of more PbF2 and PbSO4 during the pre-treatment which tend to transform to PbO2 during the following electrowinning process. In addition, the anodic layer on anode with pre-treatment in fluoride-containing H2SO4 solution is thick and compact, and its predominant composition is β-PbO2. In summary, the pre-treatment in fluoride-containing H2SO4 solution benefits the formation of a desirable protective layer in a short time.展开更多
Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius o...Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius of Na^(+)is larger than that of Li^(+),leading to challenges in its insertion/extraction at anode side.As a class of anode materials,phosphorus allotropes(PAs,red,and black) and metal phosphides(MPs) have shown great prospects because of high theoretical gravimetric/volumetric capacity,high carrier mobility,and suitable redox potential.In this review,recent developments in the studies of PAs and MPs with particular emphasis on understanding sodium storage mechanisms,developing novel synthesis strategies,and performance validations have been manifested valuable solutions to address these challenges.We begin with the introduction and classification of the macroscopic sodiation mechanisms of PAs and MPs,and the various fabrication strategies of PAs and MPs are comprehensively summarized in second section.The third section thoroughly reviews the progresses on PAs and MPs-based advanced materials for their application in SIBs.Finally,we also discuss the significant challenges and outline a roadmap for future research directions.展开更多
Silicon(Si)is a promising anode material for rechargeable batteries due to its high theoretical capacity and abundance,but its practical application is hindered by the continuous growth of porous solid-electrolyte int...Silicon(Si)is a promising anode material for rechargeable batteries due to its high theoretical capacity and abundance,but its practical application is hindered by the continuous growth of porous solid-electrolyte interphase(SEI),leading to capacity fade.Herein,a LiF-Pie structured SEI is proposed,with LiF nanodomains encapsulated in the inner layer of the organic cross-linking silane matrix.A series of advanced techniques such as cryogenic electron microscopy,time-of-flight secondary ion mass spectrometry,and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry have provided detailed insights into the formation mechanism,nanostructure,and chemical composition of the interface.With such SEI,the capacity retention of LiCoO_(2)||Si is significantly improved from 49.6%to 88.9%after 300 cycles at 100 mA g^(-1).These findings provide a desirable interfacial design principle with enhanced(electro)chemical and mechanical stability,which are crucial for sustaining Si anode functionality,thereby significantly advancing the reliability and practical application of Si-based anodes.展开更多
基金Project(50925417) supported by China National Funds for Distinguished Young ScientistsProject(50830301) supported by the National Natural Science Foundation of China+2 种基金 Project(08JJ3020) supported by the Natural Science Foundation of Hunan Province,ChinaProject(2008SK2007) supported Key Program of Science and Technology of Hunan Province,ChinaPorject(2009ZX07212-001-01) supported by Key Project for Water Pollution Control and Management Technology of China
文摘Effect of impurities in recycling water on Pb-Ag anode passivation in zinc electrowinning process was investigated by linear scan voltammetry.Results show that passivation process would be affected in the presence of Cl^-and F-in recycling water.It was highly advantageous to take H2SO4 concentration as 180g/L,Mn^2＋ concentration as 3-5 g/L and F-less than 42mg/L.However,passivation process would not be affected when Cl^-concentration was less than 13mg/L without any other ions,or when mass ratio of Mn^2＋ to Cl^-existing in electrolyte was 8,where Cl^-concentration could reach up to 625mg/L.
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Project(RDCPJ346365-06)supported by the Natural Sciences and Engineering Research Council of CanadaProject(51208193)supported by the National Natural Science Foundation of ChinaProject(11jj6034)supported by the Hunan Provincial Natural Science Foundation
文摘The effect of MnO4- and silver content on electrochemical behaviour of five commercial Pb-Ag alloy anodes was studied in acid zinc sulphate electrolyte with and without MnO4- ions at 38 °C during potential decay periods. When the anodes were immersed into acid zinc sulphate electrolyte without MnO4- ions, the Pb-0.72%Ag anode entered complete passivation state in the shortest time among the five anodes, followed by anodes Pb-0.67%Ag, Pb-0.60%Ag, Pb-0.58%Ag and Pb-0.29%Ag-0.1%Ca by measurement of open circuit potential. During immersion of the anodes, MnO4 ions accelerated the passivation and increased the corrosion current density of the anodes. After immersion in zinc electrolyte with MnO4-, the anode Pb-0.72%Ag had the best corrosion resistance, followed by anodes Pb-0.67%Ag, Pb-0.60%Ag, then the close anodes Pb-0.58%Ag and Pb-0.29%Ag-0.1%Ca by the electrochemical impedance spectroscopy （EIS） analysis.
基金supported by the Natural Sci-ence Foundation of Fujian Province (No.2024J011210)the High-Level Talent Start-Up Foundation of Xiamen Institute of Technology (No.YKJ23017R)。
文摘Aqueous sodium-ion batteries(ASIBs)have attracted great attention in aqueous batteries due to their merit of high safety.However,the constrained work potential and insufficient chemical stability of anode materials in aqueous electro-lytes hinder the large-scale application of ASIBs.Sodium titanium phosphate,NaTi_(2)(PO_(4))_(3)(NTP),is considered one of the most promising anode materials for ASIBs due to its excellent electrochemical performance and tunable structure.Recently,great achievements have been made in the development of NTP,however,a comprehensive review of existing studies is still lacking.This article firstly introduces the basic properties of NTP and analyzes the existing challenges.Subsequently,it will provide a comprehensive overview of the key strategies related to the design and modification of NTP materials with optimized electrochemical performance.Finally,based on the current research status and practical needs,suggestions,and future perspectives for advancing NTP in practical applications of ASIBs are presented.This review aims to guide the future research trajectory from basic material innovation to industrial applications,thus promoting the large-scale commercializa-tion of ASIBs.
基金financially supported by the National Natural Science Foundation of China (52272209)
文摘Niobium-based oxides show great potential in anode materials for fast-charging lithium-ion batteries,but their practical application remains hindered by intrinsically low conductivity.In this study,we successfully synthesize nano-sized Wadsley-Roth FeNb_(11)O_(29)through Fe-driven phase transformation of Nb_(2)O_(5),which delivers a high specific capacity(280.5 mA h g^(−1)at 0.25 C)along with abundant redox-active sites.Moreover,the Wadsley-Roth shear structure of FeNb_(11)O_(29)facilitates rapid Li^(+)diffusion and guarantees exceptional structural stability.Theoretical calculations further confirm that FeNb_(11)O_(29)has a narrow band gap,which significantly enhances the conductivity.Owing to these merits,FeNb_(11)O_(29)achieves a full charge/discharge cycle within merely 25 s at 75 C rate and retains remarkable cycling stability over 2500 cycles.As a consequence,our assembled FeNb_(11)O_(29)||LiFePO_(4)full cell demonstrates ultra-long cyclability(>10000 cycles)and outstanding fast-charging capability(complete cycling within 2 min at 30 C).These findings highlight nano-sized FeNb_(11)O_(29)as a highly promising anode candidate for next-generation fast-charging LIBs.
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 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support from the National Key R&D Program of China(2022YFB2402600)the National Natural Science Foundation of China(52125105,52572282,52472269,52273312,22309200)+3 种基金Guangdong Basic and Applied Basic Research Foundation(2024A1515010201,2024A1515012379,2024A1515011670,2023A1515011519)Guangdong Special Support Program Outstanding Young Talents in Science and Technology Innovation(2021TQ05L894)Shenzhen Science and Technology Planning Project(JSGG20220831104004008,SGDX20230116092055008,KCXST20221021111606016)the NSRF via the Program Management Unit for Human Resources&Institutional Development,Research and Innovation(B49G680115).
文摘Sodium-based dual-ion batteries(SDIBs)have been attracting increasing attention in recent years owing to their low cost,environmental benignancy,and high operating voltage.However,the sluggish ion kinetics of conventional carbon anodes that cannot match the fast capacitive anion intercalation behavior of graphite cathodes constraints on improving power density of SDIBs.Herein,we present an ingenious carbon microdomain engineering strategy to fabricate high-performance carbon anode with ion-mediated high-activity nitrogen species and molecular-scale closed-pore architectures.Experimental characterizations and theoretical investigations demonstrate that Zn^(2+)-mediated structural engineering tailors oxidized nitrogen species,which proficiently accelerate the sodium-ion desolvation kinetics;meanwhile the acetate-mediated pore-forming process modulates closed pores,which synergistically afford abundant sodium storage sites for high plateau-region capacity.As a result,the optimized microdomain engineered carbon material(MEC_(3))tailored with the optimal amount of zinc acetate demonstrates an outstanding plateau-region capacity of 253 mAh g^(-1)even at 1 C,among the highest reported values.Consequently,the MEC_(3)||expanded graphite dual-ion battery exhibits an unprecedented cycling stability at high current rate,maintaining 80.6%capacity retention after 10,000 cycles at 10 C,among the best reports.This microdomain engineering strategy provides a new design principle for overcoming kinetic limitations of carbonaceous materials in plateau-dominated sodium storage systems.
基金supported by the Foundation of Yunnan Province(Nos.202301AU070021,202201BE070001-027)the Test Foundation of KUST(No.2022T20210208).
文摘Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on energy storage and conversion applications,such as use as anodes in lithium-ion batteries.In this paper,all-inorganic lead-free halide perovskite Cs_(3)Bi_(2)Cl_(9)powders were synthesized by the grinding method,and the lattice was successfully adjusted via introducing Mn^(2+).The characterization results show that Mn-ion substitution can cause local lattice distortion to restructure the lattice,which will cause a mixed arrangement of[BiCl_(6)]octahedra to improve the performance of the anode material.This new material can provide a feasible solution for solving the problem of low specific capacity anode materials caused by unstable crystal structures,and also indicates that such perovskites with unique crystal structures and lattice tunability have broad application prospects in lithium-ion batteries.
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 Yunnan Province Basic Research General Program,China(No.202201BE070001-002)the Major Science and Technology Projects in Yunnan Province,China(No.202402AF 080005).
文摘The rapid expansion of the photovoltaic industry has generated heavily oxidized waste silicon(wSi),which hinders efficient recycling owing to its small particle size and uncontrolled surface oxidation.This study introduces a molten salt electrochemical strategy for converting photovoltaic wSi into NiSi_(2)-silicon nanorods(NiSi_(2)-SiNRs)as high-performance anode materials for lithium-ion batteries.A stable oxidized passivation layer is formed on the wSi surface via controlled oxidation,and further in situ generated highly active NiSi_(2) droplets.The molten salt electric field modulates the surface energy of silicon,while particle integration drives localized directional growth,enabling the self-assembly of NiSi_(2)-SiNRs composites.These NiSi_(2)-SiNRs anodes exhibit rapid ion transport and effective strain buffering.The high aspect ratio of SiNRs and the presence of retained NiSi_(2) facilitate both longitudinal and transverse Li^(+) diffusion.Owing to their robust structural design,the NiSi_(2)-SiNRs anode achieves an excellent initial Coulombic efficiency of 91.61%and retains 72.99%of its capacity after 800 cycles at 2 A·g^(−1).This study establishes a model system for investigating silicide/silicon interfaces in molten salt electrochemical synthesis and provides an effective strategy for upcycling photovoltaic wSi into high-performance lithium-ion battery anodes.
基金supported by the Basic Science Research Program(RS-2024-00455177)through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT.
文摘Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.
基金financially supported by the Research Project Supported by Shanxi Scholarship Council of China(No.2022-049)the Natural Science Foundation of Shanxi Province,China(No.20210302123167)。
文摘Carbon materials are widely recognized as highly promising electrode materials for various energy storage system applications.Coal tar residues(CTR),as a type of carbon-rich solid waste with high value-added utilization,are crucially important for the development of a more sustainable world.In this study,we employed a straightforward direct carbonization method within the temperature range of 700-1000℃to convert the worthless solid waste CTR into economically valuable carbon materials as anodes for potassium-ion batteries(PIBs).The effect of carbonization temperature on the microstructure and the potassium ions storage properties of CTR-derived carbons(CTRCs)were systematically explored by structural and morphological characterization,alongside electrochemical performances assessment.Based on the co-regulation between the turbine layers,crystal structure,pore structure,functional groups,and electrical conductivity of CTR-derived carbon carbonized at 900℃(CTRC-900H),the electrode material with high reversible capacity of 265.6m Ah·g^(-1)at 50 m A·g^(-1),a desirable cycling stability with 93.8%capacity retention even after 100 cycles,and the remarkable rate performance for PIBs were obtained.Furthermore,cyclic voltammetry(CV)at different scan rates and galvanostatic intermittent titration technique(GITT)have been employed to explore the potassium ions storage mechanism and electrochemical kinetics of CTRCs.Results indicate that the electrode behavior is predominantly governed by surface-induced capacitive processes,particularly under high current densities,with the potassium storage mechanism characterized by an“adsorption-weak intercalation”mechanism.This work highlights the potential of CTR-based carbon as a promising electrode material category suitable for high-performance PIBs electrodes,while also provides valuable insights into the new avenues for the high value-added utilization of CTR.
文摘In this work,the combined addition of strontium/indium(Sr/In)to the magnesium anode for Mg-Air Cells is investigated to improve discharge performance by modifying the anode/electrolyte interface.Indium exists as solid solution atoms in theα-Mg matrix without its second-phase generation,and at the same time facilitates grain refinement,dendritic segregation and Mg17Sr2-phases precipitation.During discharge operation,Sr modifies the film composition via its compounds and promoted the redeposition of In at the substrate/film interface;their co-deposition behavior on the anodic reaction surface enhances anode reaction kinetics,suppresses the negative difference effect(NDE)and mitigates the“chunk effect”(CE),which is contributed to uniform dissolution and low self-corrosion hydrogen evolution rate(HER).Therefore,Mg-Sr-xIn alloy anodes show excellent discharge performance,e.g.,0.5Sr-1.0In shows an average discharge voltage of 1.4234 V and a specific energy density of 1990.71 Wh kg^(-1)at 10 mA cm^(-2).Furthermore,the decisive factor(CE and self-discharge HE)for anodic efficiency are quantitively analyzed,the self-discharge is the main factor of cell efficiency loss.Surprisingly,all Mg-Sr-xIn anodes show anodic efficiency greater than 60%at high current density(≥10 mA cm^(-2)),making them excellent candidate anodes for Mg-Air cells at high-power output.
基金National Key Research and Development Program of China (2022YFB2402200)National Natural Science Foundation of China (22225201,22379028)+2 种基金Fundamental Research Funds for the Central Universities (20720220010)Shanghai Pilot Program for Basic Research–Fudan University 21TQ1400100 (21TQ009)Key Basic Research Program of Science and Technology Commission of Shanghai Municipality (23520750400)。
文摘Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials for SIBs are mainly used as cathodes because of their relatively high redox potentials(>1 V).Organic electrodes with low redox potential that can be used as anode are rare.Herein,a novel organic anode material (tetrasodium 1,4,5,8-naphthalenetetracarboxylate,Na_(4)TDC) has been developed with low redox potential (<0.7 V) and excellent cyclic stability.Its three-sodium storage mechanism was demonstrated with various in-situ/ex-situ spectroscopy and theoretical calculations,showing a high capacity of 208 mAh/g and an average decay rate of merely 0.022%per cycle.Moreover,the Na_(4)TDC-hard carbon composite can further acquire improved capacity and cycling stability for 1200 cycles even with a high mass loading of up to 20 mg cm^(-2).By pairing with a thick Na_(3)V_(2)(PO_(4))_(3)cathode (20.6 mg cm^(-2)),the as-fabricated full cell exhibited high operating voltage (2.8 V),excellent rate performance and cycling stability with a high capacity retention of 88.7% after 200 cycles,well highlighting the Na_(4)TDC anode material for SIBs.
基金the National Natural Science:Foundation of China(52375370)the Open Project of Salt Lake Chemical Engineering Research Complex,Qinghai University(2023-DXSSKF-Z02)+2 种基金the Nat-ural Science Foundation of Shanxi(202103021224049)GDAS Projects of International cooperation platform of Sci-ence and Technology(2022GDASZH-2022010203-003)Guangdong province Science and Technology Plan Projects(2023B1212060045).
文摘The dominated contradiction in optimizing the performance of magnesium-air battery anode lies in the difficulty of achieving a good balance between activation and passivation during discharge process.To further reconcile this contradiction,two Mg-0.1Sc-0.1Y-0.1Ag anodes with different residual strain distribution through extrusion with/without annealing are fabricated.The results indicate that annealing can significantly lessen the“pseudo-anode”regions,thereby changing the dissolution mode of the matrix and achieving an effective dissolution during discharge.Additionally,p-type semiconductor characteristic of discharge productfilm could suppress the self-corrosion reaction without reducing the polarization of anode.The magnesium-air battery utilizing annealed Mg-0.1Sc-0.1Y-0.1Ag as anode achieves a synergistic improvement in specific capacity(1388.89 mA h g^(-1))and energy density(1960.42 mW h g^(-1)).This anode modification method accelerates the advancement of high efficiency and long lifespan magnesium-air batteries,offering renewable and cost-effective energy solutions for electronics and emergency equipment.
基金partially supported by the National Natural Science Foundation of China(No.51901153)Shanxi Scholarship Council of China(No.2019032)+1 种基金the Natural Science Foundation of Shanxi,China(No.202103021224049)the Shanxi Zhejiang University New Materials and Chemical Research Institute Scientific Research Project,China(No.2022SX-TD025)。
文摘A novel precipitate-free Mg-0.1Sn anode with a homogeneous equal-axis grain structure was developed and rolled successfully at 573 K.Electrochemical test results indicate that the Mg-0.1Sn alloy exhibits enhanced anode dissolution kinetics.A Mg-air battery prepared using this anode exhibits a cell voltage of 1.626 V at 0.5 mA/cm^(2),reasonable anodic efficiency of 58.17%,and good specific energy of 1730.96 mW·h/g at 10 mA/cm^(2).This performance is attributed to the effective reactive anode surface,the suppressed chunk effect,and weak self-corrosion owing to the homogeneous basal texture.
基金Projects(51204208,51374240)supported by the National Natural Science Foundation of ChinaProject(2014zzts028)supported by the Fundamental Research Funds for the Central Universities of Central South University,China
文摘An attempt was made to build up a thick and compact oxide layer rapidly by pre-treating the Pb-Ag-Nd anode in fluoride-containing H2SO4 solution. The passivation reaction of Pb-Ag-Nd anode during pre-treatment process was investigated using cyclic voltammetry, linear scanning voltammetry, environmental scanning electron microscopy and X-ray diffraction analysis. The results show that Pb F2 and PbSO4 are formed near the potential of Pb/PbSO4 couple. The pre-treatment in fluoride-containing H2SO4 solution contributes to the formation of a thick, compact and adherent passive film. Furthermore, pre-treatment in fluoride-containing H2SO4 solution also facilitates the formation of PbO2 on the anodic layer, and the reason could be attributed to the formation of more PbF2 and PbSO4 during the pre-treatment which tend to transform to PbO2 during the following electrowinning process. In addition, the anodic layer on anode with pre-treatment in fluoride-containing H2SO4 solution is thick and compact, and its predominant composition is β-PbO2. In summary, the pre-treatment in fluoride-containing H2SO4 solution benefits the formation of a desirable protective layer in a short time.
基金financially supported by the Natural Science Foundation of China(Nos.22208214,22005190,and 21938005)the Science&Technology Commission of Shanghai Municipality(Nos.20QB1405700,and 19DZ1205500)Zhejiang Key Research and Development Program(No.2020C01128)
文摘Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius of Na^(+)is larger than that of Li^(+),leading to challenges in its insertion/extraction at anode side.As a class of anode materials,phosphorus allotropes(PAs,red,and black) and metal phosphides(MPs) have shown great prospects because of high theoretical gravimetric/volumetric capacity,high carrier mobility,and suitable redox potential.In this review,recent developments in the studies of PAs and MPs with particular emphasis on understanding sodium storage mechanisms,developing novel synthesis strategies,and performance validations have been manifested valuable solutions to address these challenges.We begin with the introduction and classification of the macroscopic sodiation mechanisms of PAs and MPs,and the various fabrication strategies of PAs and MPs are comprehensively summarized in second section.The third section thoroughly reviews the progresses on PAs and MPs-based advanced materials for their application in SIBs.Finally,we also discuss the significant challenges and outline a roadmap for future research directions.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB2502200)the National Natural Science Foundation of China(NSFC nos.52172257 and 22409211)+2 种基金the China Postdoctoral Science Foundation(No.2023M743739)the Postdoctoral Fellowship Program of CPSF(No.GZC20232939)CAS Youth Interdisciplinary Team。
文摘Silicon(Si)is a promising anode material for rechargeable batteries due to its high theoretical capacity and abundance,but its practical application is hindered by the continuous growth of porous solid-electrolyte interphase(SEI),leading to capacity fade.Herein,a LiF-Pie structured SEI is proposed,with LiF nanodomains encapsulated in the inner layer of the organic cross-linking silane matrix.A series of advanced techniques such as cryogenic electron microscopy,time-of-flight secondary ion mass spectrometry,and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry have provided detailed insights into the formation mechanism,nanostructure,and chemical composition of the interface.With such SEI,the capacity retention of LiCoO_(2)||Si is significantly improved from 49.6%to 88.9%after 300 cycles at 100 mA g^(-1).These findings provide a desirable interfacial design principle with enhanced(electro)chemical and mechanical stability,which are crucial for sustaining Si anode functionality,thereby significantly advancing the reliability and practical application of Si-based anodes.
